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11.
The electrophilic/nucleophilic behavior of dimethyl 2,3-dimethylenesuccinate 1, an electron-deficient 2,3-disubstituted 1,3-butadiene, in polar Diels-Alder reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The electronic nature of bonding of the transition structures involved in the cycloaddition reactions of the diene 1 toward the nucleophilically activated dienophile 6 and the strong electrophilically activated dienophile 7 has been carefully examined within the natural bond orbital (NBO) and the topological analysis of the electron localization function (ELF) frameworks. Additionally, a study of the global electrophilicity pattern of the reagents at the ground state was performed. This evidence allows us to rationalize the participation of electron-deficient 2-susbtituted and 2,3-disubstituted 1,3-butadienes as nucleophiles in polar Diels-Alder reactions. 相似文献
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Rebollar E Bounos G Oujja M Domingo C Georgiou S Castillejo M 《The journal of physical chemistry. B》2006,110(29):14215-14220
This paper investigates the influence of polymer molecular weight (M(W)) on the chemical modifications of poly(methyl methacrylate), PMMA, and polystyrene, PS, films doped with iodonaphthalene (NapI) and iodophenanthrene (PhenI), following irradiation at 248 nm (KrF excimer laser, 20 ns fwhm and hybrid excimer-dye laser, 500 fs fwhm) and at 308 nm (XeCl excimer laser, 30 ns fwhm). The changes of intensity and position of the polymer Raman bands upon irradiation provide information on cleavage of the polymer bonds. Degradation of PMMA, which is a weak absorbing system at 248 nm, occurs to a higher extent in the case of a larger M(W), giving rise to the creation of unsaturation centers and to degradation products. For highly absorbing PS, no degradation is observed upon irradiation with a KrF laser. Consistently irradiating doped PS at 308 nm, where the absorption is low, induces degradation of the polymer. Results provide direct support for the bulk photothermal model, according to which ejection requires a critical number of broken bonds. In the case of irradiation of doped PMMA with pulses of 248 nm and 500 fs, neither degradation nor dependence with polymer M(W) are observed, indicating that mechanisms involved in the femtosecond laser ablation differ from those operating in the case of nanosecond laser ablation. Participation of multiphoton/avalanche processes is proposed. 相似文献
13.
E Bellido I Ojea-Jiménez A Ghirri C Alvino A Candini V Puntes M Affronte N Domingo D Ruiz-Molina 《Langmuir : the ACS journal of surfaces and colloids》2012,28(33):12400-12409
Atomic force microscopy is shown to be an excellent lithographic technique to directly deposit nanoparticles on graphene by capillary transport without any previous functionalization of neither the nanoparticles nor the graphene surface while preserving its integrity and conductivity properties. Moreover this technique allows for (sub)micrometric control on the positioning thanks to a new three-step protocol that has been designed with this aim. With this methodology the exact target coordinates are registered by scanning the tip over the predetermined area previous to its coating with the ink and deposition. As a proof-of-concept, this strategy has successfully allowed the controlled deposition of few nanoparticles on 1 μm(2) preselected sites of a graphene surface with high accuracy. 相似文献
14.
Alicia Monleón Prof. Dr. Gonzalo Blay Prof. Dr. Luis R. Domingo Prof. Dr. M. Carmen Muñoz Prof. Dr. José R. Pedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14852-14860
A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I2, Br2 and Cl2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed. 相似文献
15.
del Puerto E Sánchez-Cortés S García-Ramos JV Domingo C 《Chemical communications (Cambridge, England)》2011,47(6):1854-1856
A possibility of getting SERS spectra of insoluble aromatic compounds in colloidal silver solutions is described. The method tested for the organic pigment quinacridone quinone consists of dispersing it in calix[n]arenes. The potentials of such cavitands, both as dispersing and as silver functionalization agents, is reported as a function of the substitution in their lower rim and their cavity size. 相似文献
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Dr. Miriam Corredor Dr. Daniel Carbajo Cecilia Domingo Dr. Yolanda Pérez Dr. Jordi Bujons Prof. Dr. Angel Messeguer Dr. Ignacio Alfonso 《Angewandte Chemie (International ed. in English)》2018,57(37):11973-11977
Despite heparin being the most widely used macromolecular drug, the design of small‐molecule ligands to modulate its effects has been hampered by the structural properties of this polyanionic polysaccharide. Now a dynamic covalent selection approach is used to identify a new ligand for heparin, assembled from extremely simple building blocks. The amplified molecule strongly binds to heparin (KD in the low μm range, ITC) by a combination of electrostatic, hydrogen bonding, and CH–π interactions as shown by NMR and molecular modeling. Moreover, this ligand reverts the inhibitory effect of heparin within an enzymatic cascade reaction related to blood coagulation. This study demonstrates the power of dynamic covalent chemistry for the discovery of new modulators of biologically relevant glycosaminoglycans. 相似文献
18.
Access to Optically Active 3‐Substituted Piperidines by Ring Expansion of Prolinols and Derivatives 下载免费PDF全文
Dr. Domingo Gomez Pardo Prof. Janine Cossy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4516-4525
The ring expansion of prolinols via an aziridinium intermediate gives C3‐substituted piperidines in good yields and enantiomeric excess, the substituent at the C3 position being derived from the most reactive nucleophile in the reaction mixture. Depending on the nucleophile, the reaction proceeds under thermodynamic or kinetic control. The regioselectivity of attack of nucleophiles on the aziridinium intermediate depends on the nature of the substituents on the nitrogen atom and the C4 position of the starting prolinols. 相似文献
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