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81.
The J = 1 ← 0 and J = 2 ← 1 transitions and the l-doubling transitions of J = 2 – 6 of 12CH3F in the ν2 and ν5 states were analyzed by taking into account the Coriolis interaction between the two modes. The molecular constants which are derived are: ν5 - ν2, 252 412 ± 112; , 25 611.60 ± 0.40; Aζ5, ?38 772 ± 116; , 25 432.52 ± 0.33; D, 21 838.4 ± 8.2; , 39.58 ± 0.30 MHz; in addition to a few other minor constants. The present result is completely consistent with the recent Raman data of Escribano, Mills, and Brodersen, J. Mol. Spectrosc.61, 249 (1976). Molecular constants in the ν3 and ν6 states have also been obtained: B3, 25 197.570 ± 0.020; B6, 25 418.917 ± 0.047; Aζ6ηJ, ?0.562 ± 0.030; |q6|, 8.70 ± 0.13 MHz. Errors are 2.5 times the standard deviations. 相似文献
82.
The cw dye laser excitation spectrum of the
vibronic transition of the HSO radical was observed between 16 420 and 16 520 cm−1 with Doppler-limited resolution, 0.03 cm−1. The HSO radical was produced by reaction of discharged oxygen with H2S or CH3SH. The observed spectra were assigned to 751 transitions of the K′a ← K″a = 2 ← 3, 1 ← 2, 0 ← 1, 1 ← 0, 2 ← 1, and 3 ← 2 subbands, and were analyzed to determine rotational constants, centrifugal distortion constants, and spin-rotation interaction constants with good precision. The signs of the spin-rotation interaction constants were determined for both the upper and the lower state from the observed spectra. The band origin obtained is 16 483.0252 (2.5σ = 0.0013) cm−1. The molecular constants which were determined reproduce the observed transitions with an average deviation of 0.0045 cm−1. 相似文献
83.
Mitsutoshi Tanimoto Shuji Saito Yasuki Endo Eizi Hirota 《Journal of Molecular Spectroscopy》1983,100(1):205-211
The microwave spectrum of the SiF radical was observed in both and of the ground vibronic state. The SiF radical was produced by a dc discharge either in a mixture or in a transient molecule SiF2 generated by the reaction of SiF4 with heated solid silicon. The latter gave twice as intense a spectrum. A least-squares fit to the observed spectrum showed the rotational constant and the centrifugal distortion constant to be 17 350.2752(63) and 0.03188(13) MHz, respectively, with three standard errors in parentheses applying to the last digits of the constants. The lambda-doubling parameter p0 was found to be negative, ?87.67 MHz, indicating that the 2Σ+ excited state contributions dominate over those of 2Σ?. All four hyperfine coupling constants a, b, c, and d were determined and were employed to discuss the unpaired-electron spin and orbital distributions in the SiF radical. 相似文献
84.
85.
Junko Hirota Dr. Kazuteru Usui Dr. Yasufumi Fuchi Masaomi Sakuma Shota Matsumoto Ryusuke Hagihara Prof. Dr. Satoru Karasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(65):14943-14952
Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines. 相似文献
86.
87.
Reflection spectra of silicate glasses were measured in the spectral region 2–13 eV. The bands due to bridging oxygen were found at 11.6 and 10.4–9.5 eV. The bands for non-bridging oxygens were found in the region 8.8–4.9 eV. They shift to lower energy with increasing ionic radius for the low valency cations while they shift to higher energy with increasing ionic radius for the high valency cations. The correlation between the measured bands and the absorption wavelength calculated from Drude-Voigt dispersion formula is discussed. 相似文献
88.
T. Kimura T. Sato M. Hirota S. Takagi 《Journal of Thermal Analysis and Calorimetry》2008,92(2):381-389
Excess enthalpies of sixteen binary mixtures between one each of methyl methylthiomethyl sulfoxide (MMTSO) and dimethyl sulfoxide
(DMSO) and one of ketone {CH3CO(CH2)nCH3, n=0 to 6 and CH3COC6H5} have been determined at 298.15 K. All the mixtures showed positive excess enthalpies over the whole range of mole fractions.
Excess enthalpies of ketone+MMTSO or DMSO increased with increasing the number of methylene radicals in the methyl alkyl ketone
molecules. Excess enthalpies of MMTSO+ketone are smaller than those of DMSO+ketone for the same ketone mixtures. The limiting
excess partial molar enthalpies of the ketone, H
1
E,∞, in all the mixtures with MMTSO were smaller than those of DMSO. Linear relationships were obtained between limiting excess
partial molar enthalpies and the number of methylene groups except 2-propanone. 相似文献
89.
Fujii T Yamaguchi S Hirota S Masuda H 《Dalton transactions (Cambridge, England : 2003)》2008,(1):164-170
Hydrogen atom abstraction reactions have been implicated in oxygenation reactions catalyzed by copper monooxygenases such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (DbetaM). We have investigated mononuclear copper(I) and copper(II) complexes with bis[(6-neopentylamino-2-pyridyl)methyl][(2-pyridyl)methyl]amine (BNPA) as functional models for these enzymes. The reaction of [Cu(II)(bnpa)]2+ with H2O2, affords a quasi-stable mononuclear copper(II)-hydroperoxo complex, [Cu(II)(bnpa)(OOH)]+ (4) which is stabilized by hydrophobic interactions and hydrogen bonds in the vicinity of the copper(II) ion. On the other hand, the reaction of [Cu(I)(bnpa)]+ (1) with O2 generates a trans-mu-1,2-peroxo dicopper(II) complex [Cu(II)2(bnpa)2(O2(2-]2+ (2). Interestingly, the same reactions carried out in the presence of exogenous substrates such as TEMPO-H, produce a mononuclear copper(II)-hydroperoxo complex 4. Under these conditions, the H-atom abstraction reaction proceeds via the mononuclear copper(II)-superoxo intermediate [Cu(II)(bnpa)(O2-)]+ (3), as confirmed from indirect observations using a spin trap reagent. Reactions with several substrates having different bond dissociation energies (BDE) indicate that, under our experimental conditions the H-atom abstraction reaction proceeds for substrates with a weak X-H bond (BDE < 72.6 kcal mol(-1)). These investigations indicate that the copper(II)-hydroperoxo complex is a useful tool for elucidation of H-atom abstraction reaction mechanisms for exogenous substrates. The useful functionality of the complex has been achieved via careful control of experimental conditions and the choice of appropriate ligands for the complex. 相似文献
90.
Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation
Akiharu Ueki Masafumi Hirota Keiko Komatsu Yutaka Takano Michio Iwaoka Hironobu Hojo Yoshiaki Nakahara 《Tetrahedron》2008,64(11):2611-2618
β-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. 相似文献