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181.
Oikawa H Fujiyoshi S Dewa T Nango M Matsushita M 《Journal of the American Chemical Society》2008,130(14):4580-4581
The fluorescence excitation spectrum of a single chromophore molecule in a photosynthetic pigment-protein complex is known to change in time at liquid helium temperature. The spectral change reflects a conformational change of the protein to which the chromophore binds. This work follows the temporal behavior of the spectrum of a single chromophore in the temperature range between 5 adn 18 K. The temperature dependence reveals two types of conformational change of the protein, i.e., thermally activated motions over a potential barrier of ca. 0.1 kJ/mol and temperature-independent motions of tunneling of a proton. 相似文献
182.
Torikai K Oishi T Ujihara S Matsumori N Konoki K Murata M Aimoto S 《Journal of the American Chemical Society》2008,130(31):10217-10226
Ladder-shaped polyether (LSP) toxins represented by brevetoxins and ciguatoxins are thought to bind to transmembrane (TM) proteins. To elucidate the interactions of LSPs with TM proteins, we have synthesized artificial ladder-shaped polyethers (ALPs) containing 6/7/6/6 tetracyclic, 6/7/6/6/7/6/6 heptacyclic, and 6/7/6/6/7/6/6/7/6/6 decacyclic systems, based on the convergent method via alpha-cyano ethers. The ALPs possessing the simple iterative structure with different numbers of rings would be useful for structure-activity relationship studies on the molecular length, which is supposed to be important when naturally occurring LSPs elicit their toxicity. Two series of ALPs were prepared to evaluate the hydrophilic or hydrophobic effects of the side chains: (i) both sides were functionalized as diols (A series), and (ii) one side remained as diol and the other side was protected as benzyl ethers (B series). To examine the interaction of these ALPs with TM proteins, dissociation of glycophorin A (GpA) dimers into monomers was evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The heptacyclic ether (ALP7B) elicited the most potent activity in the presence of 2% SDS buffer, whereas the decacyclic ether (ALP10A) exhibited an intriguing phenomenon to induce precipitation of GpA in a dose-dependent manner, under the low concentration of SDS (0.03%). ALP10A also induced precipitation of integrin alpha 1beta 1, a TM protein known to form heterodimers in the lipid bilayer membranes. The different activities among the ALPs can be accounted for by the concept of "hydrophobic matching" that is, lengths of the hydrophobic region including the side chains of ALP7B and ALP10A are ca. 25 A, which match the lengths of the hydrophobic region of alpha-helical TM proteins, as well as the hydrophobic thickness of lipid bilayer membranes. The concept of the hydrophobic matching would be a clue to understanding the interaction between LSPs and TM proteins, and also a guiding principle to design ALPs possessing potent affinities with TM proteins. 相似文献
183.
Kasai Y Matsumori N Umegawa Y Matsuoka S Ueno H Ikeuchi H Oishi T Murata M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1178-1185
Amphotericin B (AmB) is thought to exert its pharmacological effects by forming a barrel-stave assembly with ergosterol in fungal membranes. To examine the interaction between AmB and ergosterol (Erg) or cholesterol (Cho), (13)C- and (19)F-labelled covalent conjugates were prepared as reported previously (N. Matsumori et al. Chem. Biol. 2004, 11, 673-679). The CD spectra of the conjugates in a membrane-bound form suggested that the distance between the heptaene moieties of the ergosterol conjugates AmB-C(2)-(6-F)Erg 2 and AmB-C(2)-Erg 3 is similar to that of AmB in ergosterol-containing membranes, but significantly larger than that of AmB in nonsterol or cholesterol-containing membranes. These observations suggest that, as is the case with ergosterol-containing membranes, the conjugated sterol moiety prevents the close contact between the heptaene moieties within the membrane that would reduce channel conductivity of the AmB assemblies. To further investigate this bimolecular interaction, we recorded the solid-state NMR spectra of conjugates 2 and AmB-C(2)-(6-F)Cho 4, which are composed of uniformly (13)C-labelled AmB and 6-fluorinated ergosterol or cholesterol; the conjugates were expected to facilitate the estimation of distances between the fluorine and carbon atoms. By using rotor-synchronous double resonance (rotational echo double resonance of X cluster; RDX) experiments, we deduced the distance between the fluorine atom and its nearest carbon atom in the heptaene moiety of 2 to be less than 8.6 A. This indicates that the B ring of ergosterol comes close to the AmB polyene moiety. A conformational search of the AmB-ergosterol conjugate by using distance constraints derived from the RDX results suggested that ergosterol molecules possibly surround the AmB assembly, which is in contrast with the conventional image in which ergosterol is inserted into AmB molecules. 相似文献
184.
Sandberg MO Nagao O Wu Z Matsushita MM Sugawara T 《Chemical communications (Cambridge, England)》2008,(32):3738-3740
Enhancement of the electron acceptor ability of a para-quinodiimine unit by double protonation leads to the proton-induced intramolecular electron transfer from the donor unit to the cross-conjugated acceptor, giving rise to ground state triplet diradical reversibly. 相似文献
185.
Yamada M Wakahara T Tsuchiya T Maeda Y Kako M Akasaka T Yoza K Horn E Mizorogi N Nagase S 《Chemical communications (Cambridge, England)》2008,(5):558-560
Dimetallofullerene Ce(2)@C(78) and its bis-silylated derivative (1) were successfully prepared and fully characterized. 相似文献
186.
Some results about the calculation of the Choquet integral of a monotone function are presented. The construction of monotone functions from non-monotone ones that lead to the same Choquet integral is studied. 相似文献
187.
Weifang Wang Taiko Oda Remy E.P. Mangindaan Kazuyo Ukai Michio Namikoshi 《Tetrahedron》2007,63(2):409-412
Three new sulfur-containing alkaloids, polycarpaurines A (1), B (2), and C (3) were isolated from the tropical ascidian Polycarpa aurata collected in Indonesia, together with six known compounds (4-9). The structures of new compounds were assigned on the basis of their spectral data. Compounds 1, 3, 4, and 8 inhibited colony formation of Chinese hamster V79 cells with EC50 values of 6.8, 8.6, 3.8, and 10 μM, respectively. Compounds 2 and 7 showed modest activity against V79 cells (EC50>10 μM). 相似文献
188.
An ionophore antibiotic salinomycin was studied in a membrane environment consisting of isotropic bicelles, a better model for biological membranes than micelles, and its conformation and topological orientation in bicelles was determined. 2D NMR measurements and restrained conformational search revealed that salinomycin-sodium salt in bicelles adopts an open conformation in which the orientation of the E-ring is significantly different from that in crystal and solution structures. This conformational alteration breaks an intramolecular hydrogen bond between 28-OH and 1-O, dislocates the ether oxygen of the E-ring from a coordinated position to the sodium ion observed in the crystal, and consequently weakens the complexation between salinomycin and the sodium ion. Paramagnetic relaxation experiments using doxyl-phospholipids reveal that salinomycin is embedded shallowly in bicelles, with both terminals being closer to the water interface and the olefin portion facing the bicelle interior. Measurements of intermolecular NOEs between salinomycin and phospholipids further supported this orientation. Weaker complexation with sodium ion and positional preference in the membrane polar region may facilitate the catch-and-release of metal ions at the polar/nonpolar interface of bilayers. On the basis of these findings, a model for salinomycin-assisted transport of metal ions across biological membranes is proposed. 相似文献
189.
Zinc 3-hydroxymethyl-13-formyl-chlorin, 1, and its 3,13-inverted (3-formyl-13-hydroxymethyl) regioisomer, 2, and their corresponding 17,18-dehydrogenated porphyrins, 3 and 4, were synthesized for models of natural bacteriochlorophylls-c/d/e possessing 3(1)-OH and 13-C=O groups which self-aggregate in main light-harvesting antenna systems of green photosynthetic bacteria. Zinc chlorins 1 and 2 were monomers in neat THF and gave an obvious difference in their visible absorption spectra, indicating that sole inversion of the 3- and 13-substituents in a chlorin chromophore controlled their optical properties. In an aqueous Triton X-100 solution (a nonionic surfactant), zinc 3(1)-OH-13-CHO-chlorin 1 and porphyrin 3 self-aggregated as do natural bacteriochlorophylls, while zinc 3-CHO-13(1)-OH chlorin 2 and porphyrin 4 (the 3,13-inverted regioisomers of 1 and 3) hardly formed such large oligomers, showing that the inversion of the peripheral 3,13-substituents made their oligomerization unfavorable. FT-IR spectra of aggregated 1-4 in the solid film and their molecular modeling calculations suggested that the 17(2)-C=O moiety in inverted 2/4 interacted with its own 13(1)-OH group to disturb further aggregation. 相似文献
190.
Wakahara T Yamada M Takahashi S Nakahodo T Tsuchiya T Maeda Y Akasaka T Kako M Yoza K Horn E Mizorogi N Nagase S 《Chemical communications (Cambridge, England)》2007,(26):2680-2682
The (139)La NMR study of the exohedrally functionalized derivatives of La(2)@C(80) metallofullerene, La(2)@C(80)(Ar(2)Si)(2)CH(2) (: Ar = Mes, Mes = mesityl, : Ar = Dep, Dep = 2,6-diethylphenyl), reveal that the two La atoms hop between two sites along the equator of the C(80) cage. 相似文献