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91.
Dr. Julian J. Holstein Priv.‐Doz. Dr. Birger Dittrich Miriam Simon Dr. Sylvain Prévost Prof. Dr. Michael Gradzielski Prof. Dr. Guido H. Clever 《Angewandte Chemie (International ed. in English)》2018,57(41):13652-13656
A series of metal‐mediated cages, having multiple cavities, was synthesized from PdII cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd3L14] cage deriving from the tris‐monodentate ligand L1 could be quantitatively converted into its interpenetrated [5Cl@Pd6L18] dimer featuring a linear {[Pd‐Cl‐]5Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small‐angle neutron scattering (SANS) experiments showed that the cigar‐shaped assembly with a length of 3.7 nm aggregates into mono‐layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta‐cationic [5Cl@Pd6L18] cage was found to interact with polyanionic oligonucleotide double‐strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non‐covalent DNA binding. 相似文献
92.
Raoul Mens Sabine Bertho Sylvain Chambon Jan D'Haen Laurence Lutsen Jean Manca Jan Gelan Dirk Vanderzande Peter Adriaensens 《Journal of polymer science. Part A, Polymer chemistry》2011,49(7):1699-1707
The optimization and control of the nanomorphology of thin films used as active layer in bulk heterojunction (BHJ) plastic solar cells is of key importance for a better understanding of the photovoltaic mechanisms and for increasing the device performances. Hereto, solid‐state NMR relaxation experiments have been evaluated to describe the film morphology of one of the “work‐horse” systems poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene‐vinylene)/[6, 6]‐phenyl‐C61butyric acid methyl ester (MDMO‐PPV/PCBM) in a quantitative way. Attention is focused on the influence of the processing solvent (toluene vs. chlorobenzene), the blend composition, and the casting technique, that is, spin coating versus doctor blading. It is demonstrated that independently of the solvent and casting technique, part of the PCBM becomes phase separated from the mixed phase. Whereas casting from toluene results in the development of well‐defined PCBM crystallites, casting from chlorobenzene leads to the formation of PCBM‐rich domains that contain substructures of weakly organized PCBM nanoclusters. The amount and physico‐chemical state of the phase separated PCBM is quantified by solid‐state NMR relaxation times experiments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
93.
Eric Lamballais Véronique Fortuné Sylvain Laizet 《Journal of computational physics》2011,230(9):3270-3275
In this short note, we show how to use a highly accurate finite-difference scheme to compute second derivatives in the Navier–Stokes equations while ensuring targeted numerical dissipation. This approach, essentially non conservative, is shown to be close to an upwind method and is straightforward to implement with a negligible computational extra cost. The benefit offered by the resulting discrete operator is illustrated for the direct computation of sound in aeroacoustics and in the more general context of large-eddy simulation through connections with hyperviscosity and spectral vanishing viscosity. 相似文献
94.
Otfried Cheong Xavier Goaoc Andreas Holmsen Sylvain Petitjean 《Discrete and Computational Geometry》2008,39(1-3):194-212
We prove Helly-type theorems for line transversals to disjoint unit balls in ℝ
d
. In particular, we show that a family of n≥2d disjoint unit balls in ℝ
d
has a line transversal if, for some ordering ≺ of the balls, any subfamily of 2d balls admits a line transversal consistent with ≺. We also prove that a family of n≥4d−1 disjoint unit balls in ℝ
d
admits a line transversal if any subfamily of size 4d−1 admits a transversal.
Andreas Holmsen was supported by the Research Council of Norway, prosjektnummer 166618/V30. Otfried Cheong and Xavier Goaoc
acknowledge support from the French-Korean Science and Technology Amicable Relationships program (STAR). 相似文献
95.
An efficient synthesis of 9,10-disubstituted phenanthrenes is described in this Letter. These novel useful building blocks were obtained in a one-pot reaction including Suzuki-Miyaura cross-coupling followed by a Dieckmann-Thorpe ring closure under microwave irradiation. The selection of the appropriate reagents and the optimal reaction conditions to isolate the intermediate biphenyl compound or the final substituted phenanthrenes in high yields will be discussed in this Letter. 相似文献
96.
We report here several synthesis routes and their respective drawbacks/advantages for the preparation of pure LiFePO4. We demonstrate the possibility of using LiFePO4 for electrochemical applications, with respect that an effective carbon coating was realized onto the smallest particles. Actually, to bypass the weak ionic conductivity of lithium iron phosphate, the thinnest would be the particles; the highest would be the performance under severe electrochemical conditions. 相似文献
97.
98.
This work presents the synthesis of novel unsymmetrical bolaamphiphiles bearing a sugar residue and a cationic glycine betaine moiety connected to both ends of a C22 or C32 oligomethylene bridging chain possessing or not a diacetylenic unit. Preliminary transmission electron microscopy (TEM) studies revealed the polymorphism of these bola lipids with regard to their self-assembled morphologies in water depending on the presence or not of the diacetylenic functionality and on alkyl chain length. 相似文献
99.
Karim Bouchmella Sylvain G. Dutremez Dr. Christian Guérin Prof. Dr. Jean‐Christophe Longato Françoise Dahan Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2528-2536
Hydrolyses of HC?CSO3SiMe3 ( 1 ) and CH3C?CSO3SiMe3 ( 2 ) lead to the formation of acetylenic sulfonic acids HC?CSO3H?2.33 H2O ( 3 ) and CH3C?CSO3H?1.88 H2O ( 4 ). These acids were reacted with guanidinium carbonate to yield [+C(NH2)3][HC?CSO3?] ( 5 ) and [+C(NH2)3][CH3C?CSO3?] ( 6 ). Compounds 1 – 6 were characterized by spectroscopic methods, and the X‐ray crystal structures of the guanidinium salts were determined. The X‐ray results of 5 show that the guanidinium cations and organosulfonate anions associate into 1D ribbons through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions, whereas association of these ions in 6 is achieved through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) and ${{\rm R}{{1\hfill \atop 2\hfill}}}$ (6) interactions. The ribbons in 5 associate into 2D sheets through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions and ${{\rm R}{{3\hfill \atop 6\hfill}}}$ (12) rings, whereas those in 6 are connected through ${{\rm R}{{1\hfill \atop 2\hfill}}}$ (6) and ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions and ${{\rm R}{{4\hfill \atop 6\hfill}}}$ (14) rings. Compound 6 exhibits a single‐layer stacking motif similar to that found in guanidinium alkane‐ and arenesulfonates, that is, the alkynyl groups alternate orientation from one ribbon to the next. The stacking motif in 5 is also single‐layer, but due to interlayer hydrogen bonding between sulfonate anions, the alkynyl groups of each sheet all point to the same side of the sheet. 相似文献
100.
Control of degradation of polypropylene during its radical functionalisation with furan and thiophene derivatives 总被引:2,自引:0,他引:2
The traditional melt radical functionalisation of isotactic polypropylene (iPP) with maleic anhydride (MAH) and peroxide affords functionalized samples with a severe decrease of the average molecular weight (MW) due to the β-scission reaction. In this work new push-pull unsaturated molecules were investigated, consisting of a heterocyclic ring conjugated with a double bond bearing an electron attracting group. These molecules were specifically designed as MAH substitute able to limit the iPP degradation, while providing functionalisation through grafting. Butyl 3-(2-furanyl) propenoate (BFA) and butyl 3-(2-thienyl) propenoate (BTA) were comparatively tested. The analysis of the reaction products indicated that both molecules are able to graft onto the iPP backbone by prompt reaction with the macro-radicals formed through H-abstraction from iPP chains, thereby significantly limiting the MW decrease, as the functionalized macro-radicals are stabilized by resonance. Nonetheless, some of iPP macro-radicals can give a parallel chain scission before reacting with the new molecules. In the case of BFA, coupling reactions of the formed macro-radicals can lead to the formation of branched high MW architectures, whereas in the case of the thiophene derivative (BTA) only a partial retaining of polymer chain fragmentation was observed due to the reduction of β-scission. 相似文献