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91.
92.
Massoud SS Corfù NA Griesser R Sigel H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5129-5137
The first acidity constant of fully protonated xanthosine 5'-monophosphate, that is, of H3(XMP)+, was estimated by means of a micro acidity constant scheme and the following three deprotonations of the H2(XMP)+/- (pKa=0.97), H(XMP)- (5.30), and XMP2- (6.45) species were determined by potentiometric pH titrations; further deprotonation of (XMP-H)3- is possible only with pKa>12. The most important results are that the xanthine residue is deprotonated before the P(O)2(OH)- group loses its final proton; that is, twofold negatively charged XMP carries one negative charge in the pyrimidine ring and one at the phosphate group. Micro acidity constant evaluations reveal that this latter mentioned species occurs with a formation degree of 88 %, whereas its tautomer with a neutral xanthine moiety and a PO3(2-) group is formed only to 12 %; this distinguishes XMP from its related nucleoside 5'-monophosphates, like guanosine 5'-monophosphate. At the physiological pH of about 7.5 mainly (XMP-H)3- exists. The question, which of the purine sites, (N1)H or (N3)H, is deprotonated in this species cannot be answered unequivocally, though it appears that the (N3)H site is more acidic. By application of several methylated xanthine species intrinsic micro acidity constants are calculated and it is shown that, for example, for 7-methylxanthine the N1-deprotonated tautomer occurs with a formation degree of about 5 %; a small but significant amount that, as is discussed, may possibly be enhanced by metal ion coordination to N7, which is known to occur preferably to this site. 相似文献
93.
O2 was electroreduced to water, at a true-surface-area-based current density of 0.5 mA cm-2, at 37 degrees C and at pH 5 on a "wired" laccase bioelectrocatalyst-coated carbon fiber cathode. The polarization (potential vs the reversible potential of the O2 /H2O half-cell in the same electrolyte) of the cathode was only -0.07 V, approximately one-fifth of the -0.37 V polarization of a smooth platinum fiber cathode, operating in its optimal electrolyte, 0.5 M H2SO4. The bioelectrocatalyst was formed by "wiring" laccase to carbon through an electron conducting redox hydrogel, its redox functions tethered through long and flexible spacers to its cross-linked and hydrated polymer. Incorporation of the tethers increased the apparent electron diffusion coefficient 100-fold to (7.6 +/- 0.3) x 10-7 cm 2 s-1. A miniature single-compartment glucose-O2 biofuel cell made with the novel cathode operated optimally at 0.88 V, the highest operating voltage for a compartmentless miniature fuel cell. 相似文献
94.
Oana Moncea Juan Casanova‐Chafer Didier Poinsot Lukas Ochmann Clve D. Mboyi Houssein O. Nasrallah Eduard Llobet Imen Makni Molka ElAtrous Stphane Brands Yoann Rousselin Bruno Domenichini Nicolas Nuns Andrey A. Fokin Peter R. Schreiner Jean‐Cyrille Hierso 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(29):10038-10043
Diamondoids, sp3‐hybridized nanometer‐sized diamond‐like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp3‐C‐based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO2 and NH3 gases. This carbon‐based gas sensor technology allows reversible NO2 detection down to 50 ppb and NH3 detection at 25–100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p‐type sensing properties are achieved from devices based on primary phosphine–diamantanol, in which high specific area (ca. 140 m2 g?1) and channel nanoporosity derive from H‐bonding. 相似文献
95.
Dalu Chang Eric Lindberg Suihan Feng Simona Angerani Howard Riezman Nicolas Winssinger 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16179-16183
Bioluminescence resonance energy transfer (BRET) has been widely used for studying dynamic processes in biological systems such as protein–protein interactions and other signaling events. Aside from acting as a reporter, BRET can also turn on functions in living systems. Herein, we report the application of BRET to performing a biorthogonal reaction in living cells; namely, releasing functional molecules through energy transfer to a coumarin molecule, a process termed bioluminolysis. An efficient BRET from Nanoluc‐Halotag chimera protein (H‐Luc) to a coumarin substrate yields the excited state of coumarin, which in turn triggers hydrolysis to uncage a target molecule. Compared to the conventional methods, this novel uncaging system requires no external light source and shows fast kinetics (t1/2<2 min). We applied this BRET uncaging system to release a potent kinase inhibitor, ibrutinib, in living cells, highlighting its broad utility in controlling the supply of bioactive small molecules in vivo. 相似文献
96.
Werzer O Boucher N de Silva JP Gbabode G Geerts YH Konovalov O Moser A Novak J Resel R Sferrazza M 《Langmuir : the ACS journal of surfaces and colloids》2012,28(22):8530-8536
Temperature dependent structural and morphological investigations on semiconducting dioctyl-terthiophene (DOTT) thin films prepared on silica surfaces reveals the coexistence of surface induce order and distinct crystalline/liquid crystalline bulk polymorphs. X-ray diffraction and scanning force microscopy measurements indicate that at room temperature two polymorphs are present: the surface induced phase grows directly on the silica interface and the bulk phase on top. At elevated temperatures the long-range order gradually decreases, and the crystal G (340 K), smectic F (348 K), and smectic C (360 K) phases are observed. Indexation of diffraction peaks reveals that an up-right standing conformation of DOTT molecules is present within all phases. A temperature stable interfacial layer close to the silica-DOTT interface acts as template for the formation of the different phases. Rapid cooling of the DOTT sample from the smectic C phase to room temperature results in freezing into a metastable crystalline state with an intermediated unit cell between the room temperature crystalline phase and the smectic C phase. The understanding of such interfacial induced phases in thin semiconducting liquid crystal films allows tuning of crystallographic and therefore physical properties within organic thin films. 相似文献
97.
A Giuliani AR Milosavljević K Hinsen F Canon C Nicolas M Réfrégiers L Nahon 《Angewandte Chemie (International ed. in English)》2012,51(38):9552-9556
Photoionization of protein ions: The ionization energy of polyprotonated protein cations in the gas phase measured using VUV synchrotron radiation appears to be correlated with the charge state z of the protein and its tertiary structure. A simple electrostatic model accounts for the results and also shows predictive capabilities to derive a mean radius R(m) of the protein ion from the ionization energy, and vice versa. 相似文献
98.
M Oberlin R Kroemer V Mikol H Minoux E Tastan N Baurin 《Journal of chemical information and modeling》2012,52(8):2204-2214
The implementation of a structure based virtual affinity maturation protocol and evaluation of its predictivity are presented. The in silico protocol is based on conformational sampling of the interface residues (using the Dead End Elimination/A* algorithm), followed by the estimation of the change of free energy of binding due to a point mutation, applying MM/PBSA calculations. Several implementations of the protocol have been evaluated for 173 mutations in 7 different protein complexes for which experimental data were available: the use of the Boltzamnn averaged predictor based on the free energy of binding (ΔΔG(*)) combined with the one based on its polar component only (ΔΔE(pol*)) led to the proposal of a subset of mutations out of which 45% would have successfully enhanced the binding. When focusing on those mutations that are less likely to be introduced by natural in vivo maturation methods (99 mutations with at least two base changes in the codon), the success rate is increased to 63%. In another evaluation, focusing on 56 alanine scanning mutations, the in silico protocol was able to detect 89% of the hot-spots. 相似文献
99.
Anger E Srebro M Vanthuyne N Toupet L Rigaut S Roussel C Autschbach J Crassous J Réau R 《Journal of the American Chemical Society》2012,134(38):15628-15631
Introducing metal-vinyl ruthenium moieties onto [6]helicene results in a significant enhancement of the chiroptical properties due to strong metal-ligand electronic interactions. The electro-active Ru centers allow the achievement of the first purely helicene-based redox-triggered chiroptical switches. A combination of electrochemical, spectroscopic, and theoretical techniques reveals that the helicene moiety is a noninnocent ligand bearing a significant spin density. 相似文献
100.
Nicolas Dargère Véronique Bounor-Legaré Fernande Boisson Philippe Cassagnau Grégory Martin Phillipe Sonntag Nicolas Garois 《Journal of Sol-Gel Science and Technology》2012,62(3):389-396
Hydridosilazane compounds containing Si–N and Si–H bonds can be used as precursors of SiOx materials. The hydrolysis-condensation reactions of tetramethyldisilazane, as a polyhydridosilazane model compound, were
investigated by 1H and 29Si liquid NMR spectroscopy. These reactions were carried out at room temperature for up to 120 min in presence of water. The
identified products are short linear siloxane species (hydride terminated polydimethylsiloxanes MHDxMH) and cyclosiloxanes. Silicon hydride persistence in the reactional mixture suggested that silazane group is more sensitive
to hydrolysis reaction than silicon hydride group. Moreover, additional experiments evidenced that the low steric hindrance
of the silicon hydride influences the silazane hydrolysis kinetic. Hence the presence of ammonia released during silazane
hydrolysis reaction was demonstrated to be a catalyst of the silicon hydride hydrolysis reaction. 相似文献