全文获取类型
收费全文 | 3108篇 |
免费 | 83篇 |
国内免费 | 20篇 |
专业分类
化学 | 2207篇 |
晶体学 | 24篇 |
力学 | 112篇 |
综合类 | 1篇 |
数学 | 395篇 |
物理学 | 472篇 |
出版年
2024年 | 63篇 |
2023年 | 46篇 |
2022年 | 281篇 |
2021年 | 210篇 |
2020年 | 140篇 |
2019年 | 120篇 |
2018年 | 103篇 |
2017年 | 88篇 |
2016年 | 168篇 |
2015年 | 92篇 |
2014年 | 110篇 |
2013年 | 267篇 |
2012年 | 163篇 |
2011年 | 177篇 |
2010年 | 104篇 |
2009年 | 101篇 |
2008年 | 132篇 |
2007年 | 117篇 |
2006年 | 96篇 |
2005年 | 101篇 |
2004年 | 78篇 |
2003年 | 74篇 |
2002年 | 51篇 |
2001年 | 32篇 |
2000年 | 19篇 |
1999年 | 21篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 22篇 |
1995年 | 9篇 |
1994年 | 9篇 |
1993年 | 16篇 |
1992年 | 18篇 |
1991年 | 14篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 11篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 5篇 |
1973年 | 5篇 |
排序方式: 共有3211条查询结果,搜索用时 15 毫秒
61.
Dongyi Liu Ahmed M. El‐Zohry Maria Taddei Clemens Matt Laura Bussotti Zhijia Wang Jianzhang Zhao Omar F. Mohammed Mariangela Di Donato Stefan Weber 《Angewandte Chemie (International ed. in English)》2020,59(28):11591-11599
We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory. 相似文献
62.
Cystic echinococcosis (CE) or hydatid disease is a parasitic infection caused by Echinococcus granulosus. Early serodiagnosis and continuous monitoring of the disease is very important for medical treatment. Here, we report the detecting of both echinococcus antigen and antibody for the diagnosis of hydatid disease using square wave voltammetry (SWV)‐based immunosensors. The gold electrodes were functionalized using cysteamine/phenylene diisothiocyanate linkers and used for the immunosensors fabrication. The hydatid antigen and antibody immunosensors were constructed by the immobilization of either purified rabbit polyclonal antibody or recombinant antigen B (AgB), respectively on the functionalized gold electrodes surfaces. The detection in both cases was achieved by following the change in the SWV reduction peak current of the ferro/ferricyanide redox couple upon antibody or antigen binding. These immunosensors enabled the detection of echinococcus antigen and antibody within a concentration range of 1 pg.mL?1 to 1 μg.mL?1 with detection limits of 0.4 pg.mL?1 and 0.3 pg.mL?1, respectively. A preliminary application of the developed immunosensor was performed in spiked serum sample showing good recovery percentages ranging from 102 to 110 % for both hydatid antibody and antigen detection. This easy‐to‐use, sensitive, and low cost quantitative method holds great promise for the early diagnosis of hydatid disease and thus, better managements and treatment outcomes. 相似文献
63.
Huiyun Jiang Yameng Ren Weiwei Zhang Yongzhen Wu Etienne Christophe Socie Brian Irving Carlsen Jacques‐E. Moser He Tian Shaik Mohammed Zakeeruddin Wei‐Hong Zhu Michael Grtzel 《Angewandte Chemie (International ed. in English)》2020,59(24):9324-9329
Dye‐sensitized solar cells (DSSCs) based on CuII/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (VOC, more than 1 V). However, their short‐circuit photocurrent density (JSC) has remained modest. Increasing the JSC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO2 film and fast regeneration by the CuI complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers. 相似文献
64.
Kherroub Djamal Eddine Belbachir Mohammed Lamouri Saad 《Research on Chemical Intermediates》2017,43(10):5841-5856
Research on Chemical Intermediates - A new green technique to synthesize polysiloxane-type polymers is suggested based on use of chemically modified clay (Maghnite-H+) as heterogeneous,... 相似文献
65.
Abdel-Kader Maged Saad Alam Prawez Alqarni Mohammed Hamed Salkini Mohamad Ayman 《平面色谱法杂志一现代薄层色谱法》2017,30(3):211-215
JPC – Journal of Planar Chromatography – Modern TLC - A novel, simple, and sensitive high-performance thin-layer chromatography (HPTLC) method has been successfully developed and... 相似文献
66.
Zusammenfassung Es werden die Veresterungsgeschwindigkeiten der Monoaminobenzoesäuren und der 1- und 2-Pyridinkarbonsäuren bei 25° mit Chlorwasserstoff als Katalysator sowohl in wasserfreiem als auch in wasserhaltigem Glykol und in wasserfreiem Glyzerin gemessen, die derm- und derp-Aminobenzoesäure und der 2-Pyridinkarbonsäure (Nikotinsäure) auch in wasserhaltigem Glyzerin. Die Abhängigkeit der monomolekularen Geschwindigkeitskonstanten vom Wassergehalt (w) des Mediums und dem Überschuß der Konzentration der Salzsäure über die der organischen Säure, bzw. ihres Esters (C) wird für die drei zuletzt genannten Säuren durch Formeln dargestellt. Diese Geschwindigkeitskonstanten nehmen durchwegs sowohl in wasserfreiem als auch in wasserhaltigem Glykol und Glyzerin nicht nur rascher als die Konzentration der gesamten Salzsäure, sondern auch als die des obigen Überschusses, d. h. der freien Salzsäure, zu.FürC=1/3 sind beiw=0.03 die Geschwindigkeitskonstanten derm- und derp-Aminobenzoesäure und der Nikotinsäure in Äthylalkohol um 20–30 %, die der Anthranilsäure um 70%, die der Pikolinsäure um 130% größer als in Glykol, beiw=0.7 dagegen die der drei ersteren Säuren um 35–50% kleiner.In Glykol sind die Konstanten bei der Anthranilsäure und den Pyridinkarbonsäuren kleiner als in Glyzerin, bei den übrigen wie bei den früher untersuchten Säuren aber größer.Die sterische Wirkung der Aminogruppe in Orthostellung ist in Glykol größer, in Glyzerin kleiner als in Äthylalkohol.Unter gleichen Bedingungen Bind die Konstanten der Veresterungsgeschwindigkeit der Nikotinsäure in Glykol und Glyzerin etwa viermal, in Äthylalkohol nur etwa zweimal größer als die der Pikolinsäure. 相似文献
67.
Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides
下载免费PDF全文

Dr. Abdessamad Benidar Prof. Dr. Didier Bégué Dr. Falk Richter Prof. Dr. Claude Pouchan Prof. Dr. Mohammed Lahcini Dr. Jean‐Claude Guillemin 《Chemphyschem》2015,16(4):848-854
Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides. 相似文献
68.
Abdel-Ghani Boudjahem Tahar Mokrane Affef Redjel Mohammed M. Bettahar 《Comptes Rendus Chimie》2010,13(12):1433-1439
Palladium catalysts (1–10 wt.% Pd) supported on silica were prepared by hydrazine reduction of palladium chloride at room temperature. They were characterized by XRD, TEM, EDX, H2-adsorption, and H2-TPD and tested in the gas phase hydrogenation of benzene in the temperature range 75–250 °C. A conventional catalyst (1 wt.% Pd) obtained by calcination then hydrogen reduction of the same metal precursor was studied for comparison. Metal particles with a size range 6.8–28.4 nm were obtained. Dispersion, hydrogen storage and activity in benzene hydrogenation increased with decreasing particle size. In comparison, the classical catalyst was found much more dispersed (mean particle size of 1.6 nm) and more active (specific rate 1.6–3.7 times higher) than the homolog hydrazine catalyst. However, unexpectedly, turnover frequency (TOF) calculations indicated a greater reactivity of the metal surface atoms for the hydrazine catalyst. It also stored more hydrogen. These contrasting results are discussed in relation with the metal particle morphology. 相似文献
69.
The essential oil of the leaves of Cupressus sempervirens L. was isolated by hydrodistillation and tested against gram positive and gram negative bacteria, showing remarkable antimicrobial
activity against Bacillus subtilis with minimum inhibitory concentration (MIC) 75%. The antiviral activity of the essential oil was tested against Herpes simplex
virus type 1 (HSV-1), showing antiviral activity with virucidal percentages of 68.0% and 53.2% at concentrations of 1:32 and
1:64, respectively. We firstly reported the isolation of two epi-betulin esters of fatty acids from the CHCl3 fraction of Cupressus sempervirens L. leaves, which were isolated and purified using HPLC, and identified using PMR and MS. The CHCl3 fraction showed significant cytotoxicity against HeLa cells.
Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 265–268, May–June, 2009. 相似文献
70.
Serigne Massamba Seck Stéphane Charvet Modou Fall Emmanuel Baudrin Michaël Lejeune Mohammed Benlahsen 《Electroanalysis》2012,24(9):1839-1846
Nitrogenous amorphous carbon (a‐CNx) thin films were deposited by radio‐frequency cathodic magnetron sputtering (13.56 MHz) on polished and etched titanium disks. While these films are cheaper to prepare than commonly reported carbon‐based electrodes, the usable electrochemical window in aqueous solution is within the same range and spans from ?1.5 to +1.8 V vs. SCE. The electrochemical reactivity was tested using the ferri‐ferrocyanide redox couple as a function of the thin films preparation parameters. The obtained electrochemical properties allow the use of these a‐CNx thin films for stripping electroanalysis of cations in water, minimizing potential solvent reactivity. Cadmium and copper were used to test these detection abilities. Better analytical properties (notably sensitivity and linearity) were obtained as compared to a commercial boron doped diamond electrode. Preliminary competition/interaction experiments for these two cations were performed. 相似文献