全文获取类型
收费全文 | 379篇 |
免费 | 32篇 |
国内免费 | 18篇 |
学科分类
数理化 | 429篇 |
出版年
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 10篇 |
2019年 | 6篇 |
2018年 | 13篇 |
2017年 | 16篇 |
2016年 | 17篇 |
2015年 | 18篇 |
2014年 | 15篇 |
2013年 | 25篇 |
2012年 | 24篇 |
2011年 | 26篇 |
2010年 | 16篇 |
2009年 | 17篇 |
2008年 | 23篇 |
2007年 | 15篇 |
2006年 | 19篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 14篇 |
2002年 | 9篇 |
2001年 | 23篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1972年 | 4篇 |
1969年 | 2篇 |
1966年 | 1篇 |
1896年 | 1篇 |
排序方式: 共有429条查询结果,搜索用时 15 毫秒
51.
Qianqian Liu Xiaoyu Yang Meng Wang Die Liu Mingzhao Chen Tun Wu Zhiyuan Jiang Pingshan Wang 《Tetrahedron》2019,75(16):2400-2405
A novel family of metallocycles was constructed by a one-pot self-assembly of three analogous bis(terpyridine) ligand monomers L1-L3, having different bent angles, with metal ions (Zn2+ or Cd2+). The dibenzo[b,d]thiophene-containing ligand L3 assembled with the metal ions to form a single trimer, whereas the dibenzo[b,d]furan-containing ligand L2 and dibenzo[b,d]carbazole-containing ligand L1 formed a mixture of trimers and tetramers. Heteroatoms (N, O, S) significantly contributed to the molecular size of the assemblies, owing to the bent angle of the bis-terpyridines ligands. 相似文献
52.
Anodization and subsequent cathodic reactions on a thin-film sample of Zr were studied with in-situ neutron reflectometry (NR) and electrochemical impedance spectroscopy (EIS). The NR results during anodization showed the originally 485 Å thick Zr film generally behaved similar to a bulk electrode in neutral solution. The anodization ratio measured at applied potentials increased in steps of 0.5 V was somewhat higher than the value determined by coulometry, while the Pilling Bedworth ratio is in good agreement with published data. Thickening of the oxide layer, accelerated immediately after each potential increase, gradually decreased over several hours, but remained nonzero even after ~12 h. The thickened oxide eventually cracked when its thickness reached ~120 Å, causing loss of passivation. Surprisingly, neither the anodization ratio nor the Pilling Bedworth ratio showed any discontinuity at the time of oxide cracking, and the EIS behaviour remained qualitatively as before. This observation is taken as the evidence that the cracked and intact regions of the electrode behave more or less independently as parallel electrodes. When the potential was eventually switched to cathodic polarity, NR shows, as expected, that the effects of oxide cracking were irreversible. However, the electrode resistance recovered partially suggesting the cracks were rapidly plugged with newly formed oxide. 相似文献
53.
54.
55.
The inhibition efficiency of 2-aminoethanethiol (2-AEE) has been investigated against steel corrosion in 0.1 M HCl solution. The effect of temperature, pH, and concentration were studied with the help of potentiodynamic measurement, electrochemical impedance spectroscopy, scanning electron microscopy, and atomic absorption spectroscopy techniques. The potential of zero charge (Epzc) studies showed that the adsorption occurs via ?SH group; the metal surface is positively charged in corrosive test solution. The adsorptive interaction is evaluated, and best correlation was obtained with Langmuir isotherm. 2-AEE was shown to have significant inhibition efficiency against steel corrosion. The response surface methodology was employed to explain the relation between pH, inhibitor concentration, and the efficiency. The regression analysis was realized for development of an equation between independent variables and the output. The success of fitting model was tested with basic statistical arguments, residual and variance analysis, T and F tests, and R 2 value. The statistical evaluations showed that the obtained polynomial equation can be successfully used for optimization of applications involving the use of 2-AEE as inhibitor. 相似文献
56.
Dr. Hironobu Hayashi Nao Hieda Dr. Mitsuaki Yamauchi Yee Seng Chan Prof. Dr. Naoki Aratani Prof. Dr. Sadahiro Masuo Prof. Dr. Hiroko Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15079-15083
The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors ( 7-DK2 and 7-DK1 , respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation. 相似文献
57.
Emily J. Hopkins Dr. Yurii Prots Dr. Ulrich Burkhardt Dr. Yves Watier Dr. Zhiwei Hu Dr. Chang‐Yang Kuo Dr. Jen‐Che Chiang Dr. Tun‐Wen Pi Dr. Arata Tanaka Prof. Liu Hao Tjeng Dr. Martin Valldor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7938-7943
Through a solid‐state reaction, a practically phase pure powder of Ba3V2S4O3 was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P63, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated VIIIS6 and VVSO3 coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving. 相似文献
58.
Hoo Van Nguyen Naing Min Tun A. Yu. Kryukov I. M. Izvol’skii E. G. Rakov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2014,88(9):1559-1563
The “solubility” of oxidized carbon nanotubes depends on the acidity of aqueous solutions and increases drastically when pH increases from 1 (when it is almost zero) to 2. The same behavior is inherent in graphite and graphene oxides, the only difference lying in smoother increase in the solubility and in a wider range of pH. The reason for the change in solubility was shown to be cleavage of hydrogen bonds between the carboxyl groups of different particles and the behavior of the oxidized fragments (oxidation debris). It was concluded that the character of the dependences was dictated by the different geometries of nanoparticles and different distributions of carboxyl groups on their surface. 相似文献
59.
Abubakar Lawal Richard Chee Seng Wong Guan Huat Tan Lukman Bola Abdulra’uf Ali Mohamed Ali Alsharif 《Chromatographia》2018,81(5):759-768
Pesticides play vital roles in agricultural practices, but the nature and mishandling of the chemicals have led to their accumulation in moist soil, vegetables and fruits. Thus, development of efficient methods for pesticides determination is one of the most important ways to address such challenges. Multivariate response surface methodology optimisation using Placket–Burman and Box–Behnken designs were respectively used for screening and optimisation of significant factors of quick, easy, cheap, effective, rugged and safe (QuEChERS) with dispersive solid-phase extraction (SPE). Consequently, the optimised QuEChERS-dSPE technique coupled with modified ionic liquid-based (IL-based) dispersive liquid–liquid microextraction was used for sample preparation before LC–MS/MS. The developed method was validated (SANTE 11831-2017) for multi-pesticide residues determination in samples of bananas, cabbages, tomatoes, oranges and onions. The precision results were satisfactory in terms of relative standard deviation (≤?20%) as recommended. The results of accuracy for relative recoveries (82–137%) were satisfactory because 92.5% of results were within the recommended range (70–120%). The matrix effects in all the samples were very weak (less effective) (≤???80%). The linearity of the evaluated results was 5–400 µg kg?1 and regression coefficients (R2) were?>?0.99. The resulting limits of detection and quantitation were 0.02–0.32 and 0.07–1.06 µg kg?1, respectively, and therefore satisfactory. Certifiably, the estimated measurement uncertainties range (1–16%) was acceptable (≤?50%). Thus, the developed method could be reliable and suitable for routine determination of multiple pesticide residues in various vegetable and fruit samples. 相似文献
60.
High‐Temperature and High‐Energy‐Density Dipolar Glass Polymers Based on Sulfonylated Poly(2,6‐dimethyl‐1,4‐phenylene oxide)
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhongbo Zhang Dr. David H. Wang Prof. Morton H. Litt Dr. Loon‐Seng Tan Prof. Lei Zhu 《Angewandte Chemie (International ed. in English)》2018,57(6):1528-1531
A new class of high‐temperature dipolar polymers based on sulfonylated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SO2‐PPO) was synthesized by post‐polymer functionalization. Owing to the efficient rotation of highly polar methylsulfonyl side groups below the glass transition temperature (Tg≈220 °C), the dipolar polarization of these SO2‐PPOs was enhanced, and thus the dielectric constant was high. Consequently, the discharge energy density reached up to 22 J cm?3. Owing to its high Tg , the SO2‐PPO25 sample also exhibited a low dielectric loss. For example, the dissipation factor (tan δ) was 0.003, and the discharge efficiency at 800 MV m?1 was 92 %. Therefore, these dipolar glass polymers are promising for high‐temperature, high‐energy‐density, and low‐loss electrical energy storage applications. 相似文献