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61.
Masatomo Minagawa 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2307-2322
The various kinds of molecular defect that are related to the thermal property of polyacrylonitrile (PAN) are studied in detail in relation to the polymerization mechanism in an aqueous medium. The existence of two different kinds of polymer radical is pointed out and the significance of polarity of radical species is emphasized. It is shown that the structural irregularity along the main chain is surely present but has little effect on the thermal property of PAN. It is estimated that one of the most significant defects relating to the thermal property is the main-chian type of branching the occurs predominantly in hydrogen on a polymer backbone. The relationship between activator (i.e., NaHSO3) incorporation and branch inhibition mechanisms is discussed. The optimum polymerization condition, under which the highest thermal quality of molecules is obtained, is found empirically within a limited experimental range, for an aqueous heterogeneous system. 相似文献
62.
Tsukasa Akaishi Keizo Miyasaka Kinzo Ishikawa Hideki Shirakawa Sakuji Ikeda 《Journal of Polymer Science.Polymer Physics》1980,18(4):745-750
The fine structure of bulk trans-polyacetylene (PA) was investigated by x-ray diffraction. The degree of crystallinity 0.81, determined by Ruland's method, was significantly higher than the value for linear polyethylene. The disorder parameter k was 5, which is much larger than the value for polyethylene. These results led us to propose that PA crystals are more disordered than PE crystals owing to the higher rigidity of PA chains. Small-angle x-ray diffraction indicated that the crystal morphology is of the extended-chain type rather than lamellar. All results obtained in this work showed that the fine structure of PA bulk is such as to facilitate electrical conduction of bulk PA. 相似文献
63.
T. Yamabe K. Tanaka H. Terama-e K. Fukui A. Imamura H. Shirakawa S. Ikeda 《Solid State Communications》1979,29(4):329-333
The electronic structures of two possible forms of the so-called -skeletal polyacetylene (-polyacetylene) are investigated on the basis of the tight-binding LCAO-SCF-MO method under the CNDO/2 version. The analyses of the total energies per unit cell, the π bond orders and the interatomic interaction energies as to the both forms predict the -transoid backbone for the -polyacetylene. The examination of the patterns of particular molecular orbitals of the hypothetical -polymer with equal C-C bond lengths also supports the -transoid form. 相似文献
64.
Shirakawa E Hironaka K Otsuka H Hayashi T 《Chemical communications (Cambridge, England)》2006,(37):3927-3929
The combination of hexamethyldisilane and a catalytic amount of [PdCl(eta3-C3H5)]2-PPh3 was found to be effective for the trimethylsilylation of alcohols, where both of the two trimethylsilyl groups of hexamethyldisilane were transferred to alcohols without coproduction of any stoichiometric amount of byproduct but H2. 相似文献
65.
Akira Shirakawa Kazumichi Nakagawa Noriaki Itoh 《Molecular Crystals and Liquid Crystals》2013,570(3-4):211-226
The optical absorption spectra of 1-, 2- and 9-dibenzo-cyclohexadienyl radical in anthracene crystals have been obtained and analyzed. It is shown that the absorption lines consist of vibrational progression and charge-transfer lines for 2- and 9-DBCR. Each line belonging to the former has the same polarization as the most intense 0–0 vibrational line and the latter show polarization character depending on the direction of charge transfer and the transition energy was found to have a coulombic dependence on the distance of charge transfer. It is pointed out that only charge transfer lines were observed for 1-DBCR. The splitting of lines were observed and ascribed either to the resonance transfer interaction between two neighboring molecules situated at an equal distance from the radical or to the site symmetry. It is suggested that the intensity of the charge-transfer lines are borrowed from the intra-radical transition. The result that the charge transfer lines are more intense than the intra-radical lines for 1-DBCR was discussed. 相似文献
66.
Tokurakawa M Shirakawa A Ueda K Yagi H Hosokawa S Yanagitani T Kaminskii AA 《Optics letters》2008,33(12):1380-1382
Diode-pumped Kerr-lens mode-locked laser operation of Yb(3+):Lu(2)O(3) and nondoped Y(2)O(3) combined ceramics has been achieved; 65 fs pulses with an average power of 320 mW under 5 W of pump power were obtained at the center wavelength of 1032 nm. The spectral bandwidth and the time bandwidth product were 18.9 and 0.345 nm, respectively. To our knowledge, this is the first demonstration of a Kerr-lens mode-locked laser operation based on Yb(3+):Lu(2)O(3) ceramic. 相似文献
67.
M. J. Musmar M. Robert Willcott Gary E. Martin Robert T. Gampe Masatomo Iwao Milton L. Lee Ralph E. Hurd Leroy F. Johnson Raymond N. Castle 《Journal of heterocyclic chemistry》1983,20(6):1661-1669
Development of successively higher field nmr spectrometers has facilitated the study of increasingly more complex molecules, although smaller molecules such as phenanthro[3,4-b]thiophene still offer very substantial assignment problems because of the highly congested nature of their 1H- and 13C-nmr spectra. Assignments of such spectra, if they are to be unequivocal, frequently require the utilization of two-dimensional nmr spectroscopic techniques. Total assignments of the 1H- and 13C-nmr spectra of phenanthro[3,4-b]thiophene are reported. Assignments were based on a conventional high resolution 500 MHz 1H-nmr spectrum, autocorrelated two-dimensional 1H-nmr spectra (COSY), two-dimensional 1H-13C chemical shift correlation spectra and a modified version of autocorrelated 13C-13C double quantum coherence two-dimensional nmr spectroscopy. From NOE measurements, a separation of 1.99 Å between H1 and H11 was computed, suggesting that phenanthro[3,4-b]thiophene has a pronounced helical conformation in solution. 相似文献
68.
Treatment of N-heteroarylacethydrazides with an equimolar amount of nitrous acid afforded N-heteroaryacetylazides and subsequent thermolysis of these azides gave the analogues of 2,3-dihydroimidazo[1,5-a]pyridin-3-one. When some of these cyclized compounds were treated with nitrous acid, the ring opening reaction occurred and recyclized 3-(N-heteroaryl)-1,2,4-oxadiazolin-5-ones were obtained. Treatment of N-heteroarylacethydrazides with two equivalent moles of nitrous acid afforded α-oximino-α-(N-heteroaryl)acetylazides. Thermolysis of these azides gave mixtures of 3-(N-heteroaryl)-1,2,4-oxadiazolin-5-one and 3-hydroxy-4-(N-heteroaryl)furazan. On the basis of the effects of heterocyclic rings and solvents upon the relative yield of two types of the products, one plausible mechanistic explanation for the decomposition of such azides was proposed. α-Oximino-α-(H-heteroaryl)acetylazides were converted into cyano N-heterocycles by the action of alkali in good yields. 相似文献
69.
Masatomo Sumiya Yutaro Kamo Masaki Takeguchi Hideki Yoshikawa Keisuke Kobayashi Minoru Hagino Shunro Fuke 《Applied Surface Science》2010,256(14):4442-4446
Photocathode devices operating in reflection-mode, where the photoemission is detected on the same side as the light irradiation, were developed for the detection of deep ultraviolet light by using p-AlxGa1−xN films grown on Si(1 1 1) substrates. The external quantum efficiencies were as high as 20-15% at 200 nm and 280 nm, while the value was as low as 10−2% at 310 nm. The on-off ratio was more than four orders of magnitude, which represents high solar-blind sensitivity. The escape probability of AlxGa1−xN photocathode was decreased with increase of AlN mole fraction. The effective barrier potential against the photoelectron emission near the surface was reduced due to the upward shift of conduction band of AlxGa1−xN. The photoemission from the AlxGa1−xN films terminated with Cs-O adatoms will be discussed in terms of band diagrams that were evaluated by hard X-ray photoelectron spectroscopy. 相似文献
70.
Yoshiyuki Shirakawa Yusuke Hayashi Kazunori Kadota Hiroshi Mio Hiroto Ohtsuki Atsuko Shimosaka Jusuke Hidaka 《Journal of nanoparticle research》2008,10(4):577-584
In our previous paper, structural changes of selenium powders ground by a planetary ball mill at various rotational speeds
were investigated for the nanostructural modification of particles using mechanical grinding process. The experimental results
indicated that the amorphisation of Se by grinding accompanies lattice strain, and the lattice strain arises from impact energy
which is more than an energy related to intermolecular interaction. In this paper, molecular dynamics simulations of selenium
have been carried out under compressing conditions of various pressure strengths for obtaining information of the lattice
strain at atomic level. Then, dynamical behaviour of atomic configuration has been discussed in this process. The structural
disordering and formation of the structural defects were estimated by deviations of bond length and angle and the number of
created defects before and after compressing from simulated results. The disordering took place during compressing at various
pressure strengths, and the disordered atoms return to their initial positions at lower pressure. Stable disordered state
and defects after the compression can however remain by compression at more than a certain pressure strength mainly associated
with binding energy of selenium. 相似文献