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991.
Here we describe an unprecedented synthetic approach to poly(styrene)-supported chiral salen ligands by the free radical polymerization of an unsymmetrical styryl-substituted salen monomer (H2salen = bis(salicylidene)ethylenediamine). The new method allows for the attachment of salen moieties to the polymer main chain in a flexible, pendant fashion, avoiding grafting reactions that often introduce ill-defined species on the polymers. Moreover, the loading of the salen is controlled by the copolymerization of the styryl-substituted salen monomer with styrene in different ratios. The polymeric salen ligands are metallated with cobalt(II) acetate to afford the corresponding supported Co-salen complexes, which are used in the hydrolytic kinetic resolution of racemic epichlorohydrin, exhibiting high reactivity and enantioselectivity. Remarkably, the copolymer-supported Co-salen complexes showed a better catalytic performance (>99 % ee, 54 % conversion, one hour) in comparison to the homopolymeric analogues and the small molecule Co-salen complex. The soluble poly(styrene)-supported catalysts were recovered by precipitation after the catalytic reactions and were recycled three times to afford almost identical enantiomeric excesses as the first run, with slightly reduced reaction rates. 相似文献
992.
The first example of a compound containing a mixed-oxidation-state indium sub-halide complex anion, [In5Br8(quinuclidine)4]-, has been accessed by the controlled decomposition of an indium trihydride adduct, [InH3(quinuclidine)], in the presence of LiBr. An intermediate in this reaction, [InH2Br(quinuclidine)2], has been isolated and suggests that its mechanism involves hydride-bromide exchange, reductive dehydrogenation, and disproportionation processes. 相似文献
993.
Higley MN Pollino JM Hollembeak E Weck M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(10):2946-2953
A novel methodology for the formation of block copolymers has been developed that combines ring-opening metathesis polymerization (ROMP) with functional chain-transfer agents (CTAs) and self-assembly. Telechelic homopolymers of cyclooctene derivatives end-functionalized with hydrogen-bonding or metal-coordination sites are formed through the combination of ROMP with a corresponding functional CTA. These telechelic homopolymers are fashioned with a high control over molecular weight and without the need for post-polymerization procedures. The homopolymers undergo fast and efficient self-assembly with their complement homopolymer or small molecule analogue to form block-copolymer architectures. The block copolymers show equivalent association constants as their small molecule analogues described in the literature, regardless of size or nature of the complementary unit or the polymer side chain. 相似文献
994.
[reaction: see text] The alpha-hydroxycyclopentenone core structure of terpestacin has been prepared in a model system through an allene ether Nazarov cyclization of an alkylidene-gamma-butyrolactone followed by regio- and stereoselective alkylation reactions. The stereochemistry at C15 (terpestacin numbering) has been used to control stereochemistry at C1 and at C23. The use of E-alkylidene-gamma-butyrolactones extends the scope of the cationic cyclopentannelation reaction. 相似文献
995.
RuO(2)-based catalysts are much more active in the oxidation of CO than related metallic Ru catalysts. This high catalytic activity (or low activation barrier) is attributed to the weak oxygen surface bonding of bridging O atoms on RuO(2)(110) in comparison with the strongly chemisorbed oxygen on Ru(0001). Since the RuO(2)(110) surface is able to stabilize an even more weakly bound on-top oxygen species, one would anticipate that the catalytic activity will increase further under oxidizing conditions. We will show that this view is far too simple to explain our temperature-programmed reaction experiments, employing isotope labeling of the potentially active surface oxygen species on RuO(2)(110). Rather, both surface O species on RuO(2)(110) reveal similar activities in oxidizing CO. 相似文献
996.
Kumpulainen AJ Persson CM Eriksson JC Tyrode EC Johnson CM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):305-315
To examine the transition from the gaseous to the liquid-expanded monolayer state, surface tension data were recorded for n-decyl beta-d-glucopyranoside (Glu) and n-decyl beta-d-maltopyranoside (Mal) solutions at low concentrations and at different temperatures. Comparisons were also made with n-decyl beta-d-thiomaltopyranoside (S-Mal) solutions at room temperature. The transitions observed occur at very low concentrations and surface pressures, about 0.5% of the critical micelle concentration (cmc) and between 0.8 and 1 mN/m for Glu and Mal at 22 degrees C. For S-Mal the transition is recorded for a concentration of 0.5% of the cmc as well, but the surface pressure is lower, about 0.4 mN/m. The gradual change in molecular area about the transition is from about 500 to 200 A(2) and 400 to 150 A(2) for Mal and Glu, respectively, and from about 800 to 250 A(2) for S-Mal. The comparatively large molecular areas after the transitions are incompatible with the notion that a coherent hydrocarbon film would cover the entire surface already at this stage. Standard surface thermodynamics was applied to elucidate the nature of these transitions in combination with two model concepts: The formation of an infinite network of surfactant molecules and, second, the formation of surface micelles. Hard-disk simulation results were employed to quantify the additional surface pressure after the transition attributed to the formation of surface micelles. In conclusion the formation of surface micelles is plausible as the hard-disk model is capable of accounting for the additional surface pressure increase with acceptable accuracy. Further, vibrational sum frequency spectroscopy was used to investigate the transition for Mal. Using the distinct feature of the non-hydrogen-bonded OH ("free OH") at 3700 cm(-)(1) for probing the surface water state, it could be determined that the surface holds a sizable fraction of unperturbed surface water even after the transition from the Henry range. The decrease in the free OH signal was found to correlate with the increase in surface density of surface micelles. 相似文献
997.
TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed. 相似文献
998.
The acylation of 4-hydroxy-6-melhyl-2-pyrone (1) and 4-hydroxy-6-phenyl-2-pyrone (XXII) with aliphatic acid anhydrides, or with aliphatic acid chlorides in trifluoroacetic acid, has been found to product; first the corresponding ester, which then rearranges, partially or wholly, depending on the conditions and on the nature of the acyl moiety, to form the corresponding 3-acylpyrone. With aromatic acid chlorides in pyridine or in trichloroacetic acid only the corresponding ester was obtained. These esters, however, could be rearranged to the corresponding 3-acylpyrones with aluminum chloride. Acetoaeetylation of 1 and 4-hydroxycoumarin (XXIX) with diketene gave, in both cases, the C-acetoacetylated product. 相似文献
999.
[reaction: see text] Side-chain functionalized polymers possessing terminal palladated SCS pincer complexes at each repeat unit were synthesized via ring-opening metathesis polymerization. These palladium centers function as both well-defined Heck catalysts and recognition units capable of quantitative self-assembly of pyridine-containing molecules. Exploitation of both the catalytic and self-assembly properties has led to the development of a controlled, one-pot tandem catalysis/self-assembly sequence for the synthesis of functionalized polymers. 相似文献
1000.
Abstract— Chlorophyll a in aqueous hexane solutions has two fluorescence peaks, two fluorescence excitation peaks in the blue, and two fluorescence excitation peaks in the red. One of these set of peaks (excitation 2.34μ -1 and 1.52μ -1, fluorescence 1–50μ -1 ) is identical with those found in methanol solutions of chlorophyll a and is assigned to an unaggregated species, while the other set of peaks (excitation 2.44μ -1 and 1.475μ -l , fluorescence 1.48μ -l ) is assigned to a species aggregated in the presence of water. The spectral shifts occurring in the aggregate follow the selection rules obtained by McRae and Kasha for a linear stack of parallel dye molecules. The sharply increased overlap of absorption and fluorescence leads to resonance fluorescence in the aggregate. The resonance fluorescence is demonstrated experimentally. 相似文献