全文获取类型
收费全文 | 740篇 |
免费 | 28篇 |
专业分类
化学 | 465篇 |
晶体学 | 3篇 |
力学 | 14篇 |
数学 | 53篇 |
物理学 | 233篇 |
出版年
2023年 | 13篇 |
2022年 | 8篇 |
2021年 | 15篇 |
2020年 | 14篇 |
2019年 | 22篇 |
2018年 | 14篇 |
2017年 | 14篇 |
2016年 | 36篇 |
2015年 | 14篇 |
2014年 | 31篇 |
2013年 | 44篇 |
2012年 | 46篇 |
2011年 | 61篇 |
2010年 | 34篇 |
2009年 | 31篇 |
2008年 | 36篇 |
2007年 | 34篇 |
2006年 | 45篇 |
2005年 | 31篇 |
2004年 | 17篇 |
2003年 | 17篇 |
2002年 | 16篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1971年 | 3篇 |
排序方式: 共有768条查询结果,搜索用时 46 毫秒
131.
A dual pathway from readily available 2-allyl-2-carboethoxycycloalkanones 1 provides a new facile stereoselective synthesis either of functionalized spiro ketolactones 4 or of ring enlarged lactones 7 in one-step. Thus, iodination of 5-8-membered 2-allyl-2-carboethoxycycloalkanones 1a-d led, in excellent yields, to spiro ketolactones 4a-d, respectively, as single stereoisomers. On the other hand, iodination of 1a-d under alkoxy radical fragmentation conditions via incipient hemiketals produced the 8-, 9-, 10-, or 11-membered, three-atom ring enlarged, poly-functionalized lactones 7a-c as two stereoisomers and 8 as a single isomer. 相似文献
132.
Two frequency chirped continuous wave diode lasers operating in the near infrared (IR) at wavelengths of lambda approximately 1.535 microm and lambda approximately 1.520 microm have been used to measure acetylene concentrations using the P(17) and R(9) rotational lines of the (nu1 + nu3) vibrational combination band. The diode lasers were frequency chirped by applying an electrical current pulse to the laser driver at a repetition rate of greater than 1 kHz. As the laser is operated at high repetition rates, more than 1000 spectra per second can, in principle, be acquired and summed, allowing fast accumulation of data, rapid averaging and consequent improvement of the signal to noise ratio and detection limit. Experiments were performed using a single-pass cell with a path length of 16.4 cm, and also an astigmatic multi-pass absorption cell aligned to give a path length of 56 m. Detection limits corresponding to minimum detectable absorption coefficients, alpha(min), of 5.6 x 10(-5) and 7.8 x 10(-8) cm(-1), respectively, were obtained over a 4 s detection bandwidth. These detection limits would correspond to mixing ratios of 21 parts per million by volume (ppmv) and 59 parts per billion by volume (ppbv) of acetylene at 1 atm in air, with the deleterious effects of pressure broadening accounted for. The single-pass cell was used to perform breakthrough volume (BTV) experiments for the low volume adsorbent traps used to pre-concentrate organic compounds in air, taking advantage of the capability of the system to measure concentrations in real time. 相似文献
133.
Zinc micro and nanostructures were synthesized in vacuum by condensing evaporated zinc on Si substrate at different gas pressures. The morphology of the grown Zn structures was found to be dependent on the oxygen partial pressure. Depending on oxygen partial pressure it varied from two-dimensional microdisks to one-dimensional nanowire. The morphology and structural properties of the grown micro and nanostructures were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Transmission electron microscopy (TEM) studies on the grown Zn nanowires have shown that they exhibit core/shell-like structures, where a thin ZnO layer forms the shell. A possible growth mechanism behind the formation of different micro and nanostructures has been proposed. In addition, we have synthesized ZnO nanocanal-like structures by annealing Zn nanowires in vacuum at 350 °C for 30 min. 相似文献
134.
Anup Pradhan Sakhya Alo Dutta T. P. Sinha 《Applied Physics A: Materials Science & Processing》2014,114(4):1097-1104
A ceramic SmAlO3 (SAO) sample is synthesized by the solid-state reaction technique. The Rietveld refinement of the X-ray diffraction pattern has been done to find the crystal symmetry of the sample at room temperature. An impedance spectroscopy study of the sample has been performed in the frequency range from 50 Hz to 1 MHz and in the temperature range from 313 K to 573 K. Dielectric relaxation peaks are observed in the imaginary parts of the spectra. The Cole–Cole model is used to analyze the dielectric relaxation mechanism in SAO. The temperature-dependent relaxation times are found to obey the Arrhenius law having an activation energy of 0.29 eV, which indicates that polaron hopping is responsible for conduction or dielectric relaxation in this material. The complex impedance plane plot of the sample indicates the presence of both grain and grain-boundary effects and is analyzed by an electrical equivalent circuit consisting of a resistance and a constant-phase element. The frequency-dependent conductivity spectra follow a double-power law due to the presence of two plateaus. 相似文献
135.
Basudev Pradhan Steve Albrecht Burkhard Stiller Dieter Neher 《Applied Physics A: Materials Science & Processing》2014,115(2):365-369
Inverted organic solar cells are fabricated using low-temperature-annealed ZnO film as an electron transport layer. Uniform ZnO films were prepared by spin coating a diethylzinc (DEZ) precursor solution in air, followed by annealing at 100 °C. Organic solar cells prepared on these ZnO films with a 1:1 P3HT:PCBM blend as the active layer show a high power conversion efficiency of 4.03 %, which is more than 10 % higher than the PCE of solar cells comprising ZnO prepared via a high-temperature sol–gel route. 相似文献
136.
137.
The oxidation of alcohols to aldehydes using stoichiometric 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (1) in CH(2)Cl(2) at room temperature is a highly selective process favoring reaction at the carbinol center best able to accommodate a positive charge. The oxidation of aldehydes to carboxylic acids by 1 in wet acetonitrile is also selective; the rate of the process correlates with the concentration of aldehyde hydrate. A convenient and high yield method for oxidation of alcohols directly to carboxylic acids has been developed. 相似文献
138.
Gillis EA Demireva M Nanda K Beran G Williams ER Fridgen TD 《Physical chemistry chemical physics : PCCP》2012,14(10):3304-3315
Clusters of uracil (U) about a calcium dication, U(n)Ca(2+) (n = 14-4), have been studied in the gas phase by both experimental and theoretical methods. Temperature dependent blackbody infrared radiative dissociation (BIRD) experiments were performed on U(n)Ca(2+) clusters with n = 14-5 and the observed Arrhenius parameters are reported here. Master equation modeling of the BIRD kinetics data was carried out to determine threshold dissociation energies. Initial geometry calculations were performed using the B3LYP density functional and 3-21G(d) basis set. A sample of ten conformations per cluster was obtained through a simulated annealing study. These structures were optimized using B3LYP/6-31G(d) level of theory. Fragment-based hybrid many body interaction (HMBI) MP2/6-311++G(2df,2p)/Amoeba calculations were performed on representative conformations to determine theoretical binding energies. Results were examined in relation to cluster size (n). A significant increase in the energy required to remove uracil from U(6)Ca(2+) when compared to larger clusters supports previous reports that the calcium ion is coordinated by six uracil molecules in the formation of an inner shell. For clusters larger than n = 6, an odd-even alternation in threshold dissociation energies was observed, suggesting that the outer shell uracil molecules bind as dimers to the inner core. Proposed binding schemes are presented. Multiple structures of U(5)Ca(2+) are suggested as being present in the gas phase where the fifth uracil may be either part of the first or second solvation shell. 相似文献
139.
A novel ferrocene-based anion receptor bearing amide and triazolium donor groups and its anion complexation have been reported. We found that it shows marked electrochemical selectivity to F(-), followed by AcO(-) > Cl(-) > Br(-) > I(-), which is in accordance with (1)H NMR titration results. 相似文献
140.
J. Ray A.K. Biswal S. Acharya V. Ganesan D.K. Pradhan P.N. Vishwakarma 《Journal of magnetism and magnetic materials》2012
Bismuth ferrite is doped with a dilute concentration of cobalt, BiFe1−XCoXO3; X=0, 0.01, 0.02 is prepared by sol-gel auto combustion technique. X-ray diffraction data refined via Reitveld method shows single phase and shrinkage in cell volume for Co doped BiFeO3. Various magnetic ground states viz. superparamagnetic, glassy antiferromagnetic and glassy ferrimagnetic behavior is observed for X=0, 0.01, 0.02, respectively. A first-order magnetic transition is observed in the Arrott plot data of cobalt doped BiFeO3. Possibility of thermally induced magnetic transition is also seen in the magnetization data of cobalt doped BiFeO3. A model based on the existing spinoidal cyclic arrangement of spins is proposed to explain the observed data. Finally, a very dilute concentration of Co+3 in BiFeO3 is found sufficient to tailor the magnetic properties. 相似文献