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21.
The photoinitiating ability of some sulfur ylides was studied. Diphenylsulfonium bis (methoxycarbony1)methylide (DPSY) could photoinitiate methyl methacrylate and styrene. A free radical mechanism was confirmed by a kinetic study, the inhibiting effect of benzoquinone, and the copolymer composition. From an analysis of the photodecomposition products it is suggested that the phenyl radical generated from the bond fission between the sulfur atom and the phenyl group participates in the initiation of this free radical polymerization. Methylphenylsulfonium bis (methoxycarbonyl) methylide, as well as DPSY, served as a photoinitiator, but dimethylsulfonium bis (methoxycarbony1)methylide did not. The differences are explained based on UV spectra. 相似文献
22.
23.
Yue Lu Koichi Nishio Shoichi Matsuda Yuki Toshima Hiroshi Ito Tomohiro Konno Kazuhiko Ishihara Souichiro Kato Kazuhito Hashimoto Shuji Nakanishi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(8):2240-2243
There is growing awareness that circadian clocks are closely related to the intracellular redox state across a range of species. As the redox state is determined by the exchange of the redox species, electrochemically controlled extracellular electron transfer (EC‐EET), a process in which intracellular electrons are exchanged with extracellular electrodes, is a promising approach for the external regulation of circadian clocks. Herein, we discuss whether the circadian clock can be regulated by EC‐EET using the cyanobacterium Synechococcus elongatus PCC7942 as a model system. In vivo monitoring of chlorophyll fluorescence revealed that the redox state of the plastoquionone pool could be controlled with EC‐EET by simply changing the electrode potential. As a result, the endogenous circadian clock of S. elongatus cells was successfully entrained through periodically modulated EC‐EET by emulating the natural light/dark cycle, even under constant illumination conditions. This is the first example of regulating the biological clock by electrochemistry. 相似文献
24.
利用和频光谱技术详细研究了磷酸钾缓冲溶液与带负电荷的生物仿生膜(d54-DMPG磷脂双层膜)相互作用的实时过程.通过监控CD2、CD3、磷脂分子头部的磷酸根以及羰基官能团的光谱信号随加入磷酸钾缓冲溶液的实时变化,获得了磷脂双层膜分子结构的动力学变化.结果表明K+能够结合到细胞膜上,并且很快地引起了CD2、CD3、磷脂头部磷酸根以及羰基官能团信号的变化.根据各官能团的和频信号响应,磷酸钾缓冲溶液很可能是通过在双层膜中形成环形气孔来与磷脂双层膜发生作用.该结果可以很好地解释磷酸钾缓冲溶液环境下的离子协助蛋白质的跨膜过程. 相似文献
25.
Miyauchi Suguru Yamada Shuji Takeuchi Shintaro Tazaki Asahi Kajishima Takeo 《Transport in Porous Media》2022,141(1):185-199
Transport in Porous Media - A concise and accurate prediction method is required for membrane permeability in chemical engineering and biological fields. As a preliminary study on this topic, we... 相似文献
26.
Michio Iwaoka Shuji Tomoda 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):755-766
Weak nonbonded interaction between a divalent selenium and an oxygen atom (i.e., Se···O interaction) frequently plays important roles in chemical and biological functions of selenium compounds. To establish that 77 Se NMR is an easy experimental probe to diagnose the strength of an Se···O interaction, 3 series of 2-substituted benzeneselenenyl derivatives, which have an intramolecular Se···O interaction in solution, were employed. By comparing the 77 Se NMR chemical shifts (δ Se ) with those observed for other series of selenium compounds, which have an intramolecular Se···Y (Y = N, O, F, Cl, or Br) interaction, approximate linear correlation was found between the δ Se values and the strengths of the nonbonded Se···Y interactions evaluated by natural bond orbital analysis at the B3LYP level. The correlation will be useful for estimating the strength of an Se···O interaction simply from the 77 Se NMR chemical shift. By extending the chemistry of nonbonded Se···O interactions to structural biology, analogous S···O interactions have been discovered in protein architecture. The directional features were, however, different from those of Se···O and S···O interactions of small organic compounds. 相似文献
27.
Seiichi Yamamoto Shuji Koyama Chiyo Yamauchi-Kawaura Masataka Komori 《Optical Review》2017,24(3):428-435
It is commonly thought that UV or visible-light luminescence imaging of biological subjects during X-ray irradiation at the energy below 120 keV is impossible because the secondary electrons produced in this energy range do not emit Cerenkov light. Contrary to this consensus, we found UV or visible-light luminescence imaging of the subjects were possible with X-ray irradiations of this energy range. We placed one of the biological subjects in a black box; visible-light luminescence images were measured with a high-sensitivity, cooled charge coupled device (CCD) camera during X-ray irradiation at energy below 120 keV. We also conducted the imaging of air without subjects during irradiation of the same X-ray. The biological subjects emitted visible-light luminescence, and the imaging was possible with the irradiation of the X-ray below 120 keV. The luminescence images were observed in only the X-ray irradiated areas. Also air luminescence images could be obtained and the intensity of the luminescence measured from the images was proportionally increased with the exposure dose. UV or visible-light luminescence imaging of biological subjects was possible during X-ray irradiations lower energy than the Cerenkov-light threshold. The phenomenon was different from general X-ray fluorescence because wavelength of the luminescence is UV or visible-light. The luminescence imaging method is promising for estimating the irradiated area with X-ray, which could be used for interventional radiology (IVR). Also air luminescence imaging would be applied to the exposure dose distribution measurements for X-ray of diagnostic X-ray systems. 相似文献
28.
The J = 1 ← 0 and J = 2 ← 1 transitions and the l-doubling transitions of J = 2 – 6 of 12CH3F in the ν2 and ν5 states were analyzed by taking into account the Coriolis interaction between the two modes. The molecular constants which are derived are: ν5 - ν2, 252 412 ± 112; , 25 611.60 ± 0.40; Aζ5, ?38 772 ± 116; , 25 432.52 ± 0.33; D, 21 838.4 ± 8.2; , 39.58 ± 0.30 MHz; in addition to a few other minor constants. The present result is completely consistent with the recent Raman data of Escribano, Mills, and Brodersen, J. Mol. Spectrosc.61, 249 (1976). Molecular constants in the ν3 and ν6 states have also been obtained: B3, 25 197.570 ± 0.020; B6, 25 418.917 ± 0.047; Aζ6ηJ, ?0.562 ± 0.030; |q6|, 8.70 ± 0.13 MHz. Errors are 2.5 times the standard deviations. 相似文献
29.
Mitsutoshi Tanimoto Shuji Saito Yasuki Endo Eizi Hirota 《Journal of Molecular Spectroscopy》1983,100(1):205-211
The microwave spectrum of the SiF radical was observed in both and of the ground vibronic state. The SiF radical was produced by a dc discharge either in a mixture or in a transient molecule SiF2 generated by the reaction of SiF4 with heated solid silicon. The latter gave twice as intense a spectrum. A least-squares fit to the observed spectrum showed the rotational constant and the centrifugal distortion constant to be 17 350.2752(63) and 0.03188(13) MHz, respectively, with three standard errors in parentheses applying to the last digits of the constants. The lambda-doubling parameter p0 was found to be negative, ?87.67 MHz, indicating that the 2Σ+ excited state contributions dominate over those of 2Σ?. All four hyperfine coupling constants a, b, c, and d were determined and were employed to discuss the unpaired-electron spin and orbital distributions in the SiF radical. 相似文献
30.
The cw dye laser excitation spectrum of the vibronic band of HCCl was observed between 16 539 and 16 656 cm?1 with the Doppler-limited resolution, 0.03 cm?1. The HCCl molecule was generated by the reaction of discharged CF4 with CH3Cl. The observed spectra were assigned to c-type transitions with ΔKa = ±1 and also to axis-switching transitions with ΔKa = 0 or ?2, but all with K′a = 0, both for HC35Cl and HC37Cl. A rotational analysis yielded the rotational constants and quartic centrifugal distortion constants for the ground vibronic state and the band origin. A weak vibronic band, about one-third as intense as the main band, was found at about 57 cm?1 to the violet of the main band for both isotopic species, and was ascribed to a transition from the ground vibronic state to a vibrational level, possibly (041), of the à state. The rotational levels of HC35Cl in the à state showed a large perturbation; the J′ = 8, 9, and 10 levels were found to be split into two components. A normal coordinate analysis was carried out to calculate the centrifugal distortion constants and the inertia defect, which were in fair agreement with the observed values. The molecular structure of HCCl in the ground vibronic state was recalculated from the rotational constants of the two isotopic species combined with the 0.75B0 + 0.25C0 value previously reported for DC35Cl. 相似文献