全文获取类型
收费全文 | 1941篇 |
免费 | 49篇 |
国内免费 | 9篇 |
专业分类
化学 | 1497篇 |
晶体学 | 29篇 |
力学 | 23篇 |
数学 | 155篇 |
物理学 | 295篇 |
出版年
2021年 | 19篇 |
2019年 | 23篇 |
2018年 | 17篇 |
2017年 | 10篇 |
2016年 | 26篇 |
2015年 | 25篇 |
2014年 | 33篇 |
2013年 | 76篇 |
2012年 | 76篇 |
2011年 | 89篇 |
2010年 | 64篇 |
2009年 | 43篇 |
2008年 | 90篇 |
2007年 | 102篇 |
2006年 | 108篇 |
2005年 | 124篇 |
2004年 | 96篇 |
2003年 | 65篇 |
2002年 | 91篇 |
2001年 | 17篇 |
2000年 | 27篇 |
1999年 | 28篇 |
1998年 | 28篇 |
1997年 | 20篇 |
1996年 | 30篇 |
1995年 | 27篇 |
1994年 | 17篇 |
1993年 | 26篇 |
1992年 | 16篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 14篇 |
1988年 | 19篇 |
1987年 | 20篇 |
1986年 | 22篇 |
1985年 | 43篇 |
1984年 | 39篇 |
1983年 | 24篇 |
1982年 | 35篇 |
1981年 | 32篇 |
1980年 | 23篇 |
1979年 | 32篇 |
1978年 | 33篇 |
1977年 | 29篇 |
1976年 | 39篇 |
1975年 | 28篇 |
1974年 | 26篇 |
1973年 | 27篇 |
1972年 | 12篇 |
1971年 | 9篇 |
排序方式: 共有1999条查询结果,搜索用时 31 毫秒
61.
Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) (Eu[2,3-Nc(SC12H25)8]2, 1) and bis(tetra-tert-butyl-2,3- naphthalocyaninato)europium(III) (Eu[2,3-Nc(t-Bu)4]2, 2) have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3.H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV-visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2-->2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = -0.28 V (for 2) and -0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = -0.61, -1.64, -1.97, and -2.42 V, and for 1 they were observed at E1/2 = -0.62, -1.60, -1.86, and -2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared. 相似文献
62.
Valeria Balogh-Nair John D. Carriker Barry Honig Vinayak Kamat Michael G. Motto Koji Nakanishi Ranjan Sen Mordechai Sheves Maria Arnaboldi Tanis Kazuo Tsujimoto 《Photochemistry and photobiology》1981,33(4):483-488
Abstract— The difference (in cm−1 ) in absorption maxima between the protonated Schiff base of retinals and the pigment derived therefrom has been defined as the opsin shift. It represents the influence of the opsin binding site on the chromophore. The analysis of the opsin shifts of a series of dihydrobacteriorhodopsins has led to the external point-charge model, which in addition to a counter anion near the Schiff base ammonium, carries another negative charge in the vicinity of the β-ionone ring. This is in striking contrast to the external point-charge model proposed earlier for the bovine visual pigment. The absorption maxima of rhodopsins formed from bromo- and phenyl retinals support the two models. A retinal carrying a photoaffinity label has yielded a nonbleachable bacteriorhodopsin. 相似文献
63.
Extraction equilibria for the 4-(2-Pyridylazo)-Resorcinol-Nickel(II)-Quaternary-Ammonium salt system
The extraction equilibria of nickel(II)-PAR complexes with tetradecyldimethylbenzylammonium chloride(Q+Cl?) are investigated. Two kinds of nickel complex are extracted by chloroform: Ni(HR)2,nQ+Cl?(0)(?500 = 3.73·104l mol?1cm?1) at about pH 5 and 2Q+ NiR2-2(o)(?500 = 8.08·104 l mol?1 cm?1) at above pH 8.5. The extraction constant for 2Q+ NiR2-2(o) was evaluated as [2Q+ NiR2-2]0/[NiR2-2] [Q+]2 = 1011.16 at μ = 0.1 (Na2SO4. Synergic extraction studies of the Ni(HR)2 species under slightly acidic conditions show that the species is Ni(HR)2(H2O)2in auqeous solution and is extracted into chloroform as the adduct Ni(HR)2(TBP)2 (?535 = 3.57·104 l mol?1 cm?1. Based on the extraction behavior of these complexes, the structures of the Ni2+—PAR complexes are discussed. 相似文献
64.
Yasunori Inoue Hiro-o Hamaguchi Kotaro T. Yamamoto Mitsuo Tasumi Masaki Furuya 《Photochemistry and photobiology》1985,42(4):423-427
Abstract— Fluorescence spectra of native rye phytochrome were determined under different light conditions at liquid nitrogen temperature. Fluorescence spectrum of the red-light-absorbing form (Pr) had a major peak at about 685 nm (14 600 cm−1 ) and a broad sub-peak at about 515 nm (19 400 cm−1 ). The peak height at 685 nm was reduced by irradiation with monochromatic light of 640 nm, and a new peak became obvious at about 702 nm (14250 cm−1 ). This spectral change was almost completely reversed by subsequent irradiation with 700-nm light. Fluorescence spectrum of the photoequilibrium mixture of Pr and far-red-light absorbing form under continuous red light showed a sharp peak at about 685 nm having a peak height ca. 12% of Pr, and a broad sub-peak at about 508 nm (19 700 cm−1 ). Light of 730 nm did not reduce the peak height at about 685 nm but induced a new shoulder at about 699 nm (14300 cm−1 ). Monochromatic light of 640 and 700 nm given following the light of 730 nm could not reverse the spectral change at 699 nm induced by the irradiation with 730-nm light. Fluorescence spectrum of Pr in partially degraded phytochrome was similar to that in native phytochrome but the peak position in the red region was shifted by about 5 nm (100 cm−1 ) to the blue. 相似文献
65.
The ionic conduction in the perovskite-type halides, CsPbCl3, CsPbCl3 and KMnCl3, was studied. Measurements were made of ac conductivity at temperatures from 150°C to the melting point, and of ionic transport number using the Tubandt, EMF and ion-blocking methods. The effects of impurity doping on the ionic conductivity of CsPbCl3 were also studied using the samples of composition, CsPb0.99M0.01Cl2.99 (M = Li, Na, K, Ag). It was concluded that these materials are halide-ion condcutors. The ionic conductivities of CsPbCl3 and CsPbBr3 are close to those of the well known halide-ion conductors, PbCl2 and PbBr2. The ionic transport numbers were found to be > 0.9 for CsPbCl3 and CsPbBr3, and about 0.99 for KMnCl3. The conduction was considered to be caused by the migration of halide-ion vacancies VX (X = Cl, Br). The activation energies for the migration of VX were 0.29 eV for CsPbCl3, 0.25 eV for CsPbBr3 and 0.39 eV for KMnCl3. The vacancy diffusion coefficients of these materials were found to be verylarge. However, the impurity doping did not increase the ionic conductivity markedly because of small dopant solubility. 相似文献
66.
Kazuo Shimokoshi 《Chemical physics letters》1974,24(3):425-427
The gas-phase ESR technique has been used to study the xenon-photosensitization of hydrogen. The ESR spectrum of atomic hydrogen was observed when the mixtures of xenon and hydrogen were irradiated by the xenon resonance line (147 nm). The results show that photosensitized decomposition of hydrogen takes place due to the chemical quenching of the excited xenon by hydrogen molecules. 相似文献
67.
Ohno O Ikeda Y Sawa R Igarashi M Kinoshita N Suzuki Y Miyake K Umezawa K 《Chemistry & biology》2004,11(8):1059-1070
Lipopolysaccharide (LPS) is considered to cause various inflammatory reactions. We searched among microbial secondary metabolites for compounds that could inhibit LPS-stimulated adhesion between human umbilical vein endothelial cells (HUVEC) and human myelocytic cell line HL-60 cells. In the course of our screening, we isolated a novel cyclic depsipeptide, which we named heptadepsin, from the whole culture broth of Paenibacillus sp. The addition of heptadepsin prior to LPS stimulation decreased HL-60 cell-HUVEC adhesion without showing any cytotoxicity. It also inhibited the cellular adhesion induced by lipid A, the active component of LPS, but it did not inhibit TNF-alpha or IL-1beta-induced cell adhesion. The result of surface plasmon resonance (SPR) analysis revealed that heptadepsin interacted with lipid A directly. Thus, heptadepsin, a novel naturally occurring cyclic heptadepsipeptide, was shown to inactivate LPS by direct interaction with LPS. 相似文献
68.
Speciation of arsenic in body fluids 总被引:1,自引:0,他引:1
Inorganic arsenic is metabolized by consecutive reduction and methylation reactions to dimethylated arsenic (DMA), and then excreted into the urine mostly in the form of DMA. Therefore, arsenic metabolites in the body fluids and organs/tissues are present in the form of inorganic (arsenite and arsenate) and methylated arsenics (MMA and DMA). Although pentavalent arsenics can be present mostly in the form of free ions, trivalent ones may be present more in the forms conjugated with thiol groups of glutathione (GSH) or proteins. Arsenic in the body fluids (plasma, bile and urine) is present in the soluble forms and can be speciated on ion exchange columns by HPLC with on-line detection by an inductively coupled argon plasma-mass spectrometer (ICP-MS). Free forms of arsenite, arsenate, and monomethylarsonous, monomethylarsonic, dimethylarsinous and dimethylarsinic acids in the body fluids have been demonstrated to be speciated simultaneously within 10 min or so on both anion and cation exchange columns together with arsenobetaine (AsB) and arsenocholine (AsC). Trivalent arsenics conjugated with GSH were eluted in intact forms on an anion exchange column but were liberated into free forms on a cation exchange column. Thus, free and GSH-conjugated arsenic metabolites in the bile and urine have been speciated simultaneously on ion exchange columns by HPLC-ICP-MS. 相似文献
69.
Power-free poly(dimethylsiloxane) microfluidic devices for gold nanoparticle-based DNA analysis 总被引:1,自引:0,他引:1
An extremely simple, power-free pumping method for poly(dimethylsiloxane)(PDMS) microfluidic devices is presented. By exploiting the high gas solubility of PDMS, the energy for the pumping is pre-stored in the degassed bulk PDMS, therefore no additional structures other than channels and reservoirs are required. In a Y-shaped microchannel with cross section of 100 microm width x 25 microm height, this method has provided flow rate of 0.5-2 nL s(-1), corresponding to linear velocity of 0.2-0.8 mm s(-1), with good reproducibility. As an application of the power-free pumping, gold nanoparticle-based DNA analysis, which does not rely on the cross-linking mechanism between nanoparticles, has been implemented in a microchannel with three inlets. Target 15mer DNA has been easily and unambiguously discriminated from its single-base substituted mutant. Instead of colorimetric detection in a conventional microtube, an alternative detection technique suitable for microdevices has been discovered-observation of deposition on the PDMS surfaces. The channel layout enabled two simultaneous DNA analyses at the two interfaces between the three laminar streams. 相似文献
70.
Kazuo Iguchi Soichiro Kaneta Kenichiro Mori Yasuji Yamada Atsushi Honda Yo Mori 《Tetrahedron letters》1985,26(47):5787-5790
New halogenated marine prostanoids, chlorovulone I, II and III were isolated from the stolonifer Quoy and Gaimard. The structure elucidation and the antitumor activity of chlorovulones were described. 相似文献