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121.
Recyclable ionic Brönsted acid was prepared in nearly quantitative yield by reacting 1-butylimidazole with an equimolar amount of 1,3-propanesultone, followed by treatment with an equimolar amount of trifluoromethanesulfonic acid. The ionic Brönsted acid-catalyzed direct benzylation, allylation and propargylation of 1,3-dicarbonyl compounds with various alcohols in ionic liquid [N-ethyl-N-methyl imidazolium trifluoromethanesulfonate (EMIOTf)], at 100 °C for 3 h proceeded smoothly to give the corresponding products in good to excellent yields without the use of any hazardous or volatile solvents and without any by-product such as salts. Furthermore, tandem benzylation-cyclization-dehydration of 1,3-dicarbonyl compounds to give functionalized 4H-chromenes was also achieved in this catalytic reaction. 相似文献
122.
Anion recognition by 1,3-disiloxane-1,1,3,3-tetraols has been elucidated by 1H NMR titrations and ESI-MS in organic solvents. The association constants of the receptors for halide anions are larger than those of silanediol and 1,3-disiloxane-1,3-diol due to the cooperative hydrogen bonds by four silanol hydroxy groups of 1,3-disiloxane-1,1,3,3-tetraols. 相似文献
123.
Poly(N-vinylimidazole) (PVI) was synthesized by the precipitation polymerization using 2,2’-azobis(isobutyronitrile) (AIBN; initiator)
and benzene (solvent) at two different monomer/initiator ratios. The solution polymerization was also performed with the following
initiator/solvent systems: AIBN/water–methanol mixture (1:1 by volume) and 4,4’-azobis(4-cyanovaleric acid)/aqueous HCl solution
(pH 0.8). All the four preparations of PVI in ethanol and in 0.2 M NaCl (pH 3 with HCl) were examined by dynamic light scattering
(DLS). The CONTIN analysis of DLS data for each preparation from the solution polymerization showed a unimodal distribution
in both ethanol and aqueous solvents. A good agreement was obtained between the molar masses in these different solvents by
static light scattering (SLS). However, the polymers from the precipitation polymerization exhibited a heterogeneous bimodal
distribution in DLS under the same conditions as above, indicating that the SLS data as in reference [6] (Savin et al. Macromolecules 37:6565) cause a serious error in the understanding of solution behavior of PVI. 相似文献
124.
Gosuke Hayashi Masaki Hagihara Prof. Dr. Kazuhiko Nakatani Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(2):424-432
Modulation of biological networks assembled by diverse interactions among biologically active molecules has provided a platform for innovative biotechnologies. Here, we report RNA aptamers that bind to a photoresponsive peptide (KRAzR; Lys‐Arg‐azobenzene‐Arg) containing azobenzene chromophore, which can change its structure by photoirradiation. Aptamers were identified after 10 cycles of an in vitro selection procedure starting with a DNA library containing a 70 nt random region. Surface plasmon resonance (SPR) analysis demonstrated that interactions between aptamers and KRAzR were fully controlled by appropriate photoirradiation to the SPR sensor chip. Upon irradiation of 360 nm on the KRAzR‐immobilized surface, the binding of each aptamer to the surface was significantly decreased. Subsequent photoirradiation of the same surface with 430 nm restored the aptamer binding to the surface. We also observed that direct photoirradiation of the aptamer–peptide complex on a gold surface actively promoted dissociation of the complex. Furthermore, a doped reselection method was applied to acquire structural and sequence information of aptamer 66. From a data analysis of the conserved region and the mutation frequency, we were able to select a plausible secondary structure among three candidates predicted by computational folding simulation. 相似文献
125.
Vu Quoc Thang Toshiaki Taniike Masaki Umemori Mitsuhiro Ikeya Yuichi Hiraoka Nguyen Duc Nghia Minoru Terano 《大分子反应工程》2009,3(8):467-472
Preservation of initial polymer/catalyst particle morphology under air, was examined using stopped‐flow Ziegler–Natta polymerization with various quenching conditions and post‐chemical treatments. The exposure of the initial particles to air caused the fast formation of cracks on the surface, finally leading to significant reformation of the particle shape, when polymerizing particles were washed with heptane at ?65 °C under N2 or under CO2. On the other hand, when the particles were washed with heptane containing an appropriate amount of tetrahydrofuran under CO2, the particle morphology under air was almost completely maintained even after 1 h exposure. The present results are useful for various ex situ characterizations of unstable initial polymer/catalyst particles.
126.
Ogawa T Araki M Miyamae T Okayama T Hagiwara M Sakurada S Morikawa T 《Chemical & pharmaceutical bulletin》2003,51(7):759-771
To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l). 相似文献
127.
Kazuhiko Kandori Kazunao Hayashi Masaki Matsukawa Masao Fukusumi Yoshiaki Morisada 《Colloid and polymer science》2010,288(10-11):1071-1079
The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl3 solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) x –(PPO) y –(PEO) x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) x –(PEO) y –(PPO) x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N2 adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h~3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles. 相似文献
128.
Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character. 相似文献
129.
Tomonari Tanaka Masato Noguchi Masaki Ishihara Atsushi Kobayashi Shin-ichiro Shoda 《Macromolecular Symposia》2010,297(1):200-209
Summary: A cellotetraose-backboned hepta-saccharide (XXXG) (a capital X represents a glucopyranose residue that is substituted with a xylopyranose through an α-1,6 glycosidic bond, and a capital G represents a non-substituted glucopyranose residue) and a nona-saccharide (XLLG) (a capital L represents a glucopyranose residue that is substituted with a galactopyranoseβ(1-2)xylopyranose through an α-1,6 glycosidic bond) have directly been converted to the corresponding 4,6-dimethoxy-1,3,5-triazin-2-yl derivatives (DMT-β-XXXG 1 and DMT-β-XLLG 2 , respectively) by the action of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl morpholinium chloride (DMT-MM). The selective nucleophilic attack of the anomeric hydroxyl group to DMT-MM has been achieved in water without using any protection of the hydroxyl groups. The resulting activated oligosaccharide derivatives ( 1 and 2 ) were found to polymerize catalyzed by an endo-β-1,4-glucanase as catalyst. The polymerization took place in a complete regio- and stereo-selective manner, affording non-natural polysaccharides having a XXXG-repeating unit and a XLLG-repeating unit, respectively, in the main chain. It is extremely difficult to construct such definite repeating structures via the conventional synthetic routes including protection-deprotection procedures. 相似文献