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91.
Bassan A Borowski T Siegbahn PE 《Dalton transactions (Cambridge, England : 2003)》2004,(20):3153-3162
Density functional theory with the B3LYP hybrid functional has been used to study the mechanisms for dioxygen activation by four families of mononuclear non-heme iron enzymes: alpha-ketoacid-dependent dioxygenases, tetrahydrobiopterin-dependent hydroxylases, extradiol dioxygenases, and Rieske dioxygenases. These enzymes have a common active site with a ferrous ion coordinated to two histidines and one carboxylate group (aspartate or glutamate). In contrast to the heme case, this type of weak field environment always leads to a high-spin ground state. With the exception of the Rieske dioxygenases, which have an electron source outside the active site, the dioxygen activation process passes through the formation of a bridging-peroxide species, which then undergoes O-O bond cleavage finally leading to the four electron reduction of O(2). In the case of tetrahydrobiopterin- and alpha-ketoacid-dependent enzymes, the O-O heterolysis yields a high-valent iron-oxo species, which is capable of performing a two-electron oxidation chemistry on various organic substrates. For the other two families of enzymes (extradiol dioxygenases and Rieske dioxygenases) the substrate oxidation and the O-O bond cleavage are found to be coupled. In the extradiol dioxygenases the product of the O-O bond cleavage is a ferric iron with an oxy-substrate with a mixture of radical and anionic character, which is essential for the selectivity of the catechol cleavage. 相似文献
92.
Pawel Mierczynski Waldemar Maniukiewicz Tomasz P. Maniecki 《Central European Journal of Chemistry》2013,11(7):1255-1255
The original version of the article was published in Cent. Eur. J. Chem. 11(6) (2013) pp. 912–919. Unfortunately, the original version of this article contains a mistake in the Acknowledgement section. It should be written as “Partially financed from grant number 0680/B/H03/2011/40 and gratefully acknowledged. Pawe? Mierczyński is a participant of START Programme.” 相似文献
93.
Tomasz A. Modro 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):331-336
Abstract 13C NMR shielding parameters have been determined for the N-phosphorylated aniline and O-phosphorylated phenol derivatives, Ph–Y–P(O)Z2 (Y=NH, O), and for their complexes with titanium tetrachloride. Inductive and resonance substituent constants were calculated using the dsp approach for the neutral and charged substituents. The results are compared with those for the corresponding neutral and charged acetyl derivatives. Shielding effects and substituent constants are discussed in terms of the interactions of the lone pair at Y with the aromatic ring and with the acyl center. It is concluded that no significant p π-d π back-donation from Y to the phosphorus atom operates in the systems studied. 相似文献
94.
Jozsef Béres Wesley G. Bentrude Jeno Tomasz Alan E. Sopchik 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract An investigation of the effects of changing the nature of X, nitrogen base (B), and amino substituent (R2N) on the equilibrium 1?2 was carried out. The influence of the above structural changes on the time-averaged coupling constants JAP and JBP, determined at 300 MHz, were used to follow changes in Keq. With constant R2N, small effects from variation of X and B were found. A large range in Keq arose from changes in the steric size of R2N. These results will be related to the question of the ease of chair to twist interconversion of the phosphate ring essential to the biological activities of the naturally occurring diesters, cAMP and cGMP. 相似文献
95.
Bogdan Boduszek Tomasz Olszewski Waldemar Goldeman Magdalena Konieczna 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):787-795
The synthesis of a series of new pyridine aminomethylphosphinic acids is described. These compounds were obtained in the reaction of the corresponding pyridine aldehydes with primary amines and with ethyl phenylphosphinate, or methylphosphinate, in the presence of bromotrimethylsilane. In aqueous, strong acid solutions, pyridine aminophosphinic acids were split, forming the phenyl-, or methylphosphonic, acid and the corresponding secondary pyridyl-alkylamines. The kinetics of some observed cleavages were measured, and a mechanism of the cleavage has been proposed. 相似文献
96.
Jeannine Milhaud Dr. Nadia Bouchemal Dr. Tomasz Rog Dr. Edith Hantz Prof. 《Chemphyschem》2010,11(3):590-598
Phospholipid‐based reverse micelles are composed of branched cylinders. Their branching points are known to attract themselves and to slide along branches. The rate of this sliding is governed by the lifetime of H(D)‐bonded water bridges between phospholipid molecules. This lifetime is increased when the water is deuterated. On condition that the water contains at least 40 D atoms %, water/dipalmitoylphosphatidylcholine (DPPC)/deuterated pyridine reverse micelles with the composition 1.1:1:250 (v/v) have been shown to self‐organize into a liquid crystal in the 310–316 K temperature range. The mechanism of this self‐organization is unraveled by following the FTIR and 1H NMR spectra of more concentrated micelles upon heating. During the preparation of micelles, pyridine‐(D+)H+ ions are formed. They give rise to hydron transfers, under the influence of the DPPC electric charges, evidenced by two broad FTIR absorptions above (BB1) and below (BB2) the ν(C? O) stretch. These hydron transfers occur along strong (D+)H+ bonds of pyridinium ions with pyridine (BB1) and DPPC C?O groups (BB2). The proton transfers at the interface of micelles, relayed in the continuous pyridine medium, create a tenuous link between separated micelles, thus facilitating their organization. Upon heating, DPPC heads shrink and DPPC chains expand to make wedge‐shaped DPPC molecules. The micelles then change in shape: cylinders constrict and enclosed water drifts towards branching points, which swell. Branching points of neighboring micelles come into contact. Due to the deuteration of water these contacts are prolonged and H bonds are formed between DPPC molecules located in each branching point. Upon storage at 39 °C, these branching points fuse. The lateral diffusion of DPPC molecules becomes free, as evidenced by a narrowing of all 1H NMR resonances. Upon further heating, reorganization into a liquid crystal occurs. 相似文献
97.
98.
Leszek Pazderski Tomasz Pawlak Jerzy Sitkowski Lech Kozerski Edward Szłyk 《Magnetic resonance in chemistry : MRC》2010,48(6):450-457
1H, 13C and 15N NMR studies of iron(II), ruthenium(II) and osmium(II) tris‐chelated cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline of the general formula [M(LL)3]2+ (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature 1H signal assignments were corrected. Significant shielding of nitrogen‐adjacent protons [H(6) in bpy, H(2) in phen] and metal‐bonded nitrogens was observed, being enhanced in the series Ru(II) → Os(II) → Fe(II) for 1H, Fe(II) → Ru(II) → Os(II) for 15N and bpy → phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) → Os(II) → Fe(II). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
99.
Wojciech Marynowski Tomasz Klucznik Katarzyna Baranowska Anna Dołęga Dr. Wiesław Wojnowski 《无机化学与普通化学杂志》2010,636(5):685-687
Tri(mesityloxy)silanethiol (TMST) was isolated as the only product of the reaction between SiS2 and 2,4,6‐trimethylphenol. TMST crystallizes in the triclinic system. Good quality of the crystal allowed the unrestricted refinement of the mercapto group; the resulting S–H distance is 1.29(4) Å and the Si–S–H bond angle is 95.4(17)°. Molecules of TMST show no hydrogen bonds in the crystal – the FT‐IR spectrum of the solid sample exhibits a very sharp, well‐resolved band of isolated –SH group at 2562 cm–1. 相似文献
100.
Tuzimski T 《Journal of AOAC International》2010,93(6):1748-1756
The application of TLC with a diode array detector (TLC-DAD) and HPLC-DAD after SPE for identification and quantitative analysis of pesticides in water samples is demonstrated. The procedures described for the determination of compounds are inexpensive and can be applied to routine analysis of analytes in water samples after preliminary cleanup and concentration by SPE. Average recoveries for four different cartridges and three solvents by the proposed HPLC-DAD method after SPE also are presented. The efficiency of the SPE procedure was evaluated using real water samples from the Zemborzycki Reservoir, near Lublin, southeastern Poland. The method was validated for precision, repeatability, and accuracy. 相似文献