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121.
trans- and cis-1-(4-Dimethylaminophenyl)-6-(4-nitrophenyl)hex-3-ene-1,5-diynes (trans- and cis-DANE) were synthesized and their photochemical properties were studied. The absorption spectra of trans-DANE red-shifted compared with the parent compound bisphenylethynylethene (BEE) due to intramolecular charge transfer. The fluorescence spectra, Stokes shift, fluorescence lifetime, fluorescence quantum yield, and quantum yield of trans-to-cis photoisomerization of trans-DANE showed strong dependence upon the solvent polarity in the less-polar region. No fluorescence emission from trans-DANE was observed in medium-polar and polar solvents. The quantum yield of cis-to-trans isomerization was almost solvent independent. The donor-acceptor substituents shifted the equilibrium between the trans perpendicular triplet state and the trans planar triplet state to the trans triplet state, and resulted in an increase in the triplet lifetime. Comparison of the photochemical properties of trans-DANE with trans-4-dimethylamino-4'-nitrostilbene (DANS) suggests that trans-DANE is a possible fluorescent probe in the non-polar region. 相似文献
122.
Nakamura K Suzuki T Hasegawa M Kato Y Sasaki H Inouye K 《Journal of chromatography. A》2003,1009(1-2):133-139
An affinity sorbent, hydrophilic polymer-based carrier of different pore size (Toyopearl) with immobilized p-aminobenzamidine (ABA), has been prepared. Its basic properties and some applications for protein purification were studied. ABA, which is a synthetic inhibitor for trypsin-like proteases, was covalently immobilized to Toyopearl by reductive amination. The ligand density and binding capacity for porcine trypsin varied depending on the pore size of Toyopearl. The maximum binding capacity of the immobilized p-aminobenzamidine Toyopearl (ABA-Toyopearl) for trypsin was more than 40 mg/ml gel. ABA-Toyopearl thus obtained was very stable below pH 8 and was successfully used for high-performance affinity chromatography of trypsin-like proteases such as trypsin, thrombin, tissue-type plasminogen activator or urokinase in a single step at 25 degrees C. 相似文献
123.
K. Kondo H. Kawabata S. Ueda H. Hasegawa O. Mitamura Y. Seike J. Inaba Y. Ohmomo 《Journal of Radioanalytical and Nuclear Chemistry》2004,260(1):81-87
A nuclear fuel reprocessing facility is currently under construction in Rokkasho Village, Aomori, Japan. After completion
and start-up, this facility will discharge radionuclides into the Pacific Ocean through an outlet pipe set on the seafloor
offshore. For future assessments of the stability of these radionuclides in the environment, a sufficient understanding of
the behavior of radionuclides in this ocean ecosystem before the start-up of the facility is necessary. To understand the
processes by which radionuclides and various other types of elements are eliminated from seawater, we measured the sedimentation
flux of suspended particles in the coastal waters off Rokkasho Village where the sea emissions pipes will be placed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
124.
Goto K Yano Y Okada E Liu CW Yamamoto K Ueoka R 《The Journal of organic chemistry》2003,68(3):865-870
Specific acid catalysis of p-sulfonatocalix[n]arenes (n = 4, Calix-S4; n = 6, Calix-S6; n = 8, Calix-S8) was observed in the alcoholysis of N-acetyl-l-amino acids in methanol. The methanolysis rates of basic amino acid substrates (His, Lys, and Arg) were markedly enhanced in the presence of Calix-Sn, as compared with rates observed with p-hydroxybenzenesulfonic acid (pHBS), which is a noncyclic analogue of Calix-Sn. This catalytic effect of Calix-Sn was not observed for the methanolysis of Phe, Tyr, and Trp substrates. On the other hand, (1)H NMR experiments following the effect of Calix-Sn on N-acetyl-l-amino acid substrates in CD(3)OD showed that the spectrum of a mixture of the His substrate with Calix-Sn was significantly different from the combined spectra of the respective compounds. These changes in spectra support the formation of an inclusion complex of Calix-Sn with basic amino acids. Furthermore, it was obvious that methanolysis of the His substrate catalyzed by Calix-S4 and Calix-S6 obeyed Michaelis-Menten kinetics. These results indicate that the catalytic activity of Calix-Sn originates from its forming a complex with specific substrates (basic amino acids), similar to enzymatic reactions. 相似文献
125.
Shoichi Katsuta Tokutaro Kimura Yoshihiro Kudo Ryozo Nakagawa Yasuyuki Takeda Mikio Ouchi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(2):89-98
The overall extraction constants (Kex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheKex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The Kex valuedecreases in the orders Ag+ > Na+ >Tl+ > K+ > Li+ andPb2+ > Ba2+ > Sr2+ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant. 相似文献
126.
Hiroshi Tanaka Tsuyoshi Hasegawa Narumi Kita Hiroko Nakahara Takahiro Shibata Sho Oe Makoto Ojika Koji Uchida Takashi Takahashi 《化学:亚洲杂志》2006,1(5):669-677
An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ12,14‐PGJ2 (15dPGJ2) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ2 derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ2 derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ2 derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ2 derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ2. 相似文献
127.
K. Norisuye K. Okamura Y. Sohrin H. Hasegawa T. Nakanishi 《Journal of Radioanalytical and Nuclear Chemistry》2005,267(1):183-193
Summary The present paper describes a new analytical method for determining the 240Pu/239Pu isotopic ratio and 238Pu/239+240Pu α -activity ratio in seawater, both of which are important parameters for determining Pu sources in the ocean. Plutonium
isotopes were preconcentrated from a large volume of seawater (4700-10800 liter) by solid phase extraction using MnO2-impregnated fibers and eluted into 3M HCl. After the elution, the Pu species of all oxidation states were converted to Pu(IV)
using NaNO2, purified by solvent extraction using thenoyltrifluoroacetone (TTA)-benzene, and concentrated in 5 ml of 0.2M HNO2. The 240Pu/239Pu and 238Pu/239+240Pu ratios in the 5-ml final solution were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and α-spectrometry,
respectively. A pg level of Pu, which was a sufficiently large amount for the determination, was obtained by the solid phase
extraction. Through the redox conversion and solvent extraction, the Pu species, such as Pu(III), Pu(IV) and Pu(VI), were
collected at a high recovery of 96±2% (n=3) despite the presence of large amounts of Mn, and interfering 238U (3.3 μg. l-1in seawater) was effectively removed with a decontamination factor of 1.7·107. The accuracy of the method for the 240Pu/239Pu ratio was verified using reference materials of seawater and a terrestrial soil sample. The present technique was applied
to the determination of the 240Pu/239Pu and 238Pu/239+240Pu ratios in coastal and oceanic water. 相似文献
128.
PULSE RADIOLYSIS STUDIES IN MODEL LIPID SYSTEMS: FORMATION AND BEHAVIOR OF PEROXY RADICALS IN FATTY ACIDS 总被引:1,自引:0,他引:1
Abstract— Radiolytic formation and peroxidation of fatty acid radicals have been investigated by pulse radiolysis techniques in oleate, linoleate, linolenate and arachidonate systems. A strong absorption band at 280 nm associated with conjugated radicals, Rconj , formed in polyunsaturated fatty acid moieties has been used as a probe for kinetic processes occurring at doubly allylic sites in the hydrocarbon chain. Formation of Rconj by O- has been found to be more efficient than the less selective OH radical. Peroxidation of Rconj is shown to be somewhat slower, ( k R + O2 ˜ 3 × 108 M -1 s-1 ), than O2 reactions with radicals in oleate ( k R + O2 = 1 × 109 M -1 s-1 ). Peroxy radicals generated in these reactions disappear slowly by essentially second order processes (2 k RO1 ˜ 107 M -1 s-1 ). The superoxide radical, O- 2 , shows little if any reactivity towards 0.01 M linolenate or arachidonate over periods of 20 s. 相似文献
129.
Nakanishi M Eguchi A Akuta T Nagoshi E Fujita S Okabe J Senda T Hasegawa M 《Current protein & peptide science》2003,4(2):141-150
Improving the performance of non-viral gene-delivery vehicles that consist of synthetic compounds and nucleic acids is a key to successful gene therapy. Supplementing synthetic vehicles with various biological functions by using natural or artificial peptides is a promising approach with which to achieve this goal. One of the obstacles hindering this effort is that some of the potentially useful peptides, especially those with many basic amino acid residues, interfere with the formation of the complex owing to strong electrostatic interactions with the nucleic acid. In this review, we describe our recent work in examining the potential of these peptides in gene delivery, using a recombinant lambda phage particle as the model for the gene-delivery complex. Lambda phage encapsulates large duplex DNA in a rigid polyplex-like shell with a diameter of 55 nm, and can display various peptides on this capsid, independently of particle formation. By examining the expression of marker genes encapsulated in the phage capsid, we have demonstrated that the protein transduction domain of HIV Tat protein and the nuclear localization signal derived from SV40 T antigen can remarkably facilitate the delivery of these marker genes across the two major barriers, the cell membrane and the nuclear membrane, respectively. Our results indicate that these basic peptides can constitute effective components of synthetic gene-transfer complexes, as long as sufficient copies are displayed on the outer surface of the complex. 相似文献
130.
Abstract A memory type PDLC has been prepared by sandwiching a mixture of two-frequency-addressing liquid crystals and acrylate monomers with a hydoroxy group between two glass substrates with ITO electrodes followed by UV irradiation. This PDLC can be electrically switched between a transparent state and a light scattering state, which are maintained over several months without electric fields. 相似文献