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101.
Quantitative structure-activity relationships (QSARs) based on the octanol/water partition coefficient were employed to predict acute toxicities of 36 substituted aromatic compounds and their mixtures. In this study, the model developed by Verhaar et al. was modified and used to calculate octanol/water partition coefficients of chemical mixtures. To validate the model, acute toxicities of these chemicals were measured to Vibrio fischeri in terms of EC50. The results indicated that the obtained QSAR models could be used to predict toxicities of samples consisting of these substituted aromatic compounds, individually or in combinations. The obtained equations were proved to be robust enough by using the leave-one-out test method. By classifying these chemicals into two groups, polar and non-polar, the toxicities of chemical mixtures within each group can be predicted accurately from their calculated partition coefficients. 相似文献
102.
FT‐IR spectroscopic and thermodynamic measurements were designed to explore the effect of a macromolecular crowder, dextran, on the temperature and pressure‐dependent phase diagram of the protein Ribonuclease A (RNase A), and we compare the experimental data with approximate theoretical predictions based on configuration entropy. Exploring the crowding effect on the pressure‐induced unfolding of proteins provides insight in protein stability and folding under cell‐like dense conditions, since pressure is a fundamental thermodynamic variable linked to molecular volume. Moreover, these studies are of relevance for understanding protein stability in deep‐sea organisms, which have to cope with pressures in the kbar range. We found that not only temperature‐induced equilibrium unfolding of RNase A, but also unfolding induced by pressure is markedly prohibited in the crowded dextran solutions, suggesting that crowded environments such as those found intracellularly, will also oppress high‐pressure protein unfolding. The FT‐IR spectroscopic measurements revealed a marked increase in unfolding pressure of 2 kbar in the presence of 30 wt % dextran. Whereas the structural changes upon thermal unfolding of the protein are not significantly influenced in the presence of the crowding agent, through stabilization by dextran the pressure‐unfolded state of the protein retains more ordered secondary structure elements, which seems to be a manifestation of the entropic destabilization of the unfolded state by crowding. 相似文献
103.
Mingqiang Li Shixian Lv Zhaohui Tang Wantong Song Haiyang Yu Hai Sun Huaiyu Liu Xuesi Chen 《Macromolecular bioscience》2013,13(9):1150-1162
Rapid and efficient side‐chain functionalization of polypeptide with neighboring carboxylgroups is achieved via the combination of ring‐opening polymerization and subsequent thiol‐yne click chemistry. The spontaneous formation of polymersomes with uniform size is found to occur in aqueous medium via electrostatic interaction between the anionic polypeptide and cationic doxorubicin hydrochloride (DOX·HCl). The polymersomes are taken up by A549 cells via endocytosis, with a slightly lower cytotoxicity compared with free DOX ·HCl. Moreover, the drug‐loaded polymersomes exhibit the enhanced therapeutic efficacy, increase apoptosis in tumor tissues, and reduce systemic toxicity in nude mice bearing A549 lung cancer xenograft, in comparison with free DOX ·HCl. 相似文献
104.
Jiangmei Li Haiyun Zhai Zuanguang Chen Qing Zhou Zhenping Liu Zihao Su 《Journal of separation science》2013,36(21-22):3608-3614
A novel method combining molecular imprinting and SPE was developed in a capillary column for the determination of auramine O in shrimp. The capillary monolithic column was prepared by UV‐initiated in situ polymerization, using auramine O as template and methacrylic acid and ethylene dimethacrylate as functional monomer and cross‐linker, respectively. The properties of the prepared capillary monolithic column were investigated under the optimized conditions coupled with HPLC, and then the morphologies of the inner polymers were characterized by SEM. The calibration curve was expressed as A = 103C + 19.8 (r = 0.9992) with a linear range of 0.25–25.0 μg/mL, and the recoveries of auramine O at different concentrations in shrimp ranged from 90.5 to 92.4% with RSDs ranging from 2.1 to 4.4%. The capacities of the molecularly imprinted polymer and nonimprinted polymer columns were 0.722 and 0.147 μg/mg, respectively, and the LOD (S/N = 3) of auramine O in shrimp was 17.85 μg/kg. Under the selected conditions, the enrichment factors obtained were higher than 70‐fold. The results indicate that the prepared molecularly imprinted capillary monolithic column was reliable and applicable to the analysis of auramine O in shrimp. 相似文献
105.
Due to the synthetic flexibility and special enantioselectivity, chiral ionic liquids (CILs) have heightened interest and an increasing number of CILs has been designed and utilized. In this work, CIL named l-1-butyl-3-(2-propionic-1-ether) imidazolium bromide ([BAlaIM]Br) derived from natural amino acids was synthesized, with chiral center at cation moiety. Chiral stationary phases for gas chromatography were then prepared by mixing the CIL with polymeric ionic liquid ([PSOMIM][NTf2], homemade) at different ratios (4:1, 2:1, and 1:1). The column efficiency was measured to be about 3,200 plates m?1 (8 m × 0.25 mm i.d.) when the content of [BAlaIM]Br was 50 % (mass percent) in the mixed stationary phase. All columns were coated via the static coating method using 0.30 % (w/v) of stationary phases dissolved in methanol. The results showed that the CIL contributed to the selectivity of stationary phase toward positional isomers dichlorobenzenes, methylnaphthalenes and pinenes, etc. Meanwhile, [BAlaIM]Br showed better selectivity for enantiomers such as carvones, citronellals, limonenes and camphors. The interactions between chiral selector and enantiomers were also discussed. 相似文献
106.
A practical method for the preparation of cycloalkenyl boronic acid pinacol esters is described. These important synthetic intermediates are typically made using more expensive methods like transition metal-catalyzed borylation of alkenyl halides or triflates. In this work, they are obtained from the simple corresponding cycloalkanones, which are subjected to Shapiro reaction conditions followed by trapping with a borate ester. The requisite products are obtained in very good to excellent yields, and the reactions can be scaled up to multigram amounts. By providing a simple alternative to common methods that make use of expensive transition-metal catalysts and formation of sensitive intermediates, this convenient method will be useful for the synthesis of ring-containing partners for Suzuki–Miyaura cross-coupling and other reactions employing boronic esters as substrates. 相似文献
107.
Ranran Du Bingbing Suo Huixian Han Yibo Lei Gaohong Zhai 《International journal of quantum chemistry》2013,113(22):2464-2470
Potential energy curves of 22 electronic states of RhN have been calculated by the complete active space second‐order perturbation theory method. The X1Σ0+ is assigned as the ground state, and the first excited state a3Π0+ is 978 cm?1 higher. The 1Δ(I) and B1Σ+ states are located at 9521 and 13,046 cm?1 above the ground state, respectively. The B1Σ+ state should be the excited state located 12,300 cm?1 above the ground state in the experimental study. Moreover, two excited states, C1Π and b3Σ+, are found 14,963 and 15,082 cm?1 above the X1Σ+ state, respectively. The transition C1Π1–X1Σ0+ may contribute to the experimentally observed bands headed at 15,071 cm?1. There are two excited states, D1Δ and E1Σ+, situate at 20,715 and 23,145 cm?1 above the X1Σ+ state. The visible bands near 20,000 cm?1 could be generated by the electronic transitions D1Δ2–a3Π1 and E1Σ+0–X1Σ+0 because of the spin–orbit coupling effect. © 2013 Wiley Periodicals, Inc. 相似文献
108.
Synthesis of 2-cinnamoyl-1-styryl-3,4-diarylcyclopentanol via cyclodimerization of 1,5-diaryl-1,4-pentadien-3-one mediated by zinc was carried out in good yields at room temperature in NH4Cl (aq.) and tetrahydrofuran under ultrasonic irradiation. In comparison with conventional methods, the main advantages of the present procedure are shorter reaction time and better yields. 相似文献
109.
Xiaoyu Dong Liang Cui Yunjing Shi Shilie Pan Zhongxiang Zhou Zhihua Yang Bingbing Zhang Xiangzhan Jiang Yun Yang Zhaohui Chen Zhenjun Huang 《无机化学与普通化学杂志》2013,639(6):988-993
The single crystals of Ba2Cd(B3O6)2 were grown by the spontaneous crystallization method for the first time. They crystallize in the centrosymmetric trigonal space group R$\bar{3}$ with a = 7.143(3) Å, c = 17.405(16) Å, and Z = 3. The structure is characterized by isolated B3O6 units, and the Ba2+ and Cd2+ cations connect with B3O6 rings to form three dimensional structure. The TG/DSC and XRD results reveal that Ba2Cd(B3O6)2 melts congruently. First‐principles electronic structure calculation performed with the density functional theory (DFT) method shows that the calculated bandgaps are 4.66 eV, which is in good agreement with the UV/Vis/NIR experimental value 4.59 eV. The calculation shows that the Ba2Cd(B3O6)2 crystal has a large birefringence (Δn = 0.0875–0.0569 from 270 nm to 2600 nm), which demonstrates that Ba2Cd(B3O6)2 is a potential birefringence crystal. 相似文献
110.
The polyaniline of different intrinsic oxidation states, viz., the emeraldine (EM) and the leucoemeraldine (LM) states, were coated on 3‐aminopropyltriethoxy silane modified fly ash cenospheres. Without prior sensitization by SnCl2 solution, Pd activation by PdCl2 solution was carried out on EM and LM laden cenospheres, followed by electroless plating of copper (Cu). The topography and composition of the composites were characterized by scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy, etc. The results indicate that the oxidation state of the LM layer showed a much bigger increase than that of the EM layer in the Pd activation process, while coupled Pd reduction underwent to a more extent on the LM layer. The metallic Pd atoms on the LM and EM layers surface initiated the subsequent electroless plating of Cu, and the coated Cu on LM laden cenospheres had a much more uniform and compact morphology than that on EM laden cenospheres. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献