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51.
The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 . 相似文献
52.
Dan Donescu Sever Serban Kristiana Gosa Cristian Petcu 《Central European Journal of Chemistry》2005,3(1):10-27
The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl
acrylate) (PEtA) with TiO2 was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved
simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl
acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane
derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl
acetate (VAc). The PVAc-TiO2 hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane
derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly
affected by TiO2 presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of
TiO2 inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network. 相似文献
53.
Masashi Hamaguchi Kazuma TakahashiTakumi Oshima Hatsue Tamura 《Tetrahedron letters》2003,44(23):4339-4342
Reactions of tricarbonyl compounds with vinyl diazo compounds 2 were carried out. Reaction of 1,2,3-indanetrione with 2a,b,c gave the spiroindan-1,3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl compounds 1,2,3-trioxo-2,3-dihydrophenalene 11 and dimethylalloxane 13 gave the dioxole 12 and the dihydrofuran 14, respectively, typical products expected from vinyl carbonyl ylides. 相似文献
54.
Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior. 相似文献
55.
56.
To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization
of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium
persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration
compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization.
Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was
observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the
end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles.
From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion
radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA.
Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen
abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen
abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical
to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of
hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Received: 26 April 2001 Accepted: 6 September 2001 相似文献
57.
The inducing method for preparing Ag-micelle solution with the use of mixed solvent/nonsolvent, and the morphological characterization of the generated metal–micelles were investigated and reported in this paper. In this method, an Ag containing metal chelate polymer (MCP) raw solution was preprepared by dissolving poly(vinyl acetate) (PVAc)–silver nitrate (AgNO3) MCP in conc. formic acid, and a mixed solvent of HCOOH/H2O with specific water composition was then added to induce the micellization of the MCP chain. The critical water concentration (CWC) that was needed for inducing the formation of the Ag-micelles, and the water concentration at which the flocculation of the Ag-micelles occurred in micellar solution, were studied by measuring the transmittance of the dilute MCP solution; the results showed that a long-lasting MCP solution with stable micelles might be prepared by using a H2O/HCOOH solvent of specific weight ratio 1:1.2. The effect of the AgNO3 concentration on the morphology of the Ag-micelles was also investigated by transmission electron microscopy (TEM). At AgNO3 concentration below 0.5 wt%, the Ag-micelles displayed a variety of core-shell structure; but as the AgNO3 concentration was increased to 1.0–2.0 wt%, micelles that had Ag-solid embedded in the micellar core were observed. 相似文献
58.
Ahmed Abd El-Fattah Mohamad Nageeb Hassan Ahmad Rashad Mona Marei Sherif Kandil 《International Journal of Polymer Analysis and Characterization》2020,25(5):362-373
Abstract An injectable composite hydrogel composed of polyvinyl alcohol (PVA) and bioactive glass (BG) particles were synthesized by a physical crosslinking approach. The morphology, mechanical properties, and viscoelasticity of the PVA/BG composite hydrogel were characterized. Scanning electronic microscopy (SEM) showed uniform and homogeneous distribution of BG particles throughout the composite hydrogel. The incorporation of 2.5?wt% of BG particles in the composite hydrogel formulations, enhanced the static compressive strength and static elastic modulus by 325% and 150%, respectively. The storage molds (G′) was greater than the loss modules (G′′) at all the frequency range studied, which revealed a self-standing elastic composite hydrogel with a smooth injectability. The PVA/BG composite hydrogel was also implanted subcutaneously in the dorsal region of adult male rats. After 4?weeks of implantation, no inflammatory cells were seen within and around the implant, which indicated that the composite hydrogel was biocompatible. The properties of the synthesized injectable PVA/BG composite hydrogel demonstrate its capability toward bone regeneration. 相似文献
59.
60.
Ioanna Chalari Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1519-1526
The synthesis of second‐generation (G‐2) dendritic polymers of isoprene (I) and styrene (S) was achieved with anionic polymerization high‐vacuum techniques and by performing the following steps: (1) selective reaction of a living chain with the chlorosilane group of 4‐(chlorodimethylsilyl)styrene (a dual‐functionality compound) to produce a macromonomer, (2) addition of a second living chain (same or different) to the double bond of the macromonomer, (3) polymerization of I with the anionic sites, and (4) reaction of the produced off‐center living species with trichloromethyl silane or tetrachlorosilane (CH3SiCl3 or SiCl4). The combined characterization results showed that the G‐2 dendritic macromolecules synthesized—(S2I)3, (SI′I)3, (I″I′I)3, (I′2I)4—have a high molecular and compositional homogeneity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1519–1526, 2002 相似文献