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21.
    
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity.  相似文献   
22.
The spin polarized β-emitting nuclei12B (I π=1+,T 1/2=20.18 ms) were produced by the nuclear reaction11B(d, p)12B and by the selection technique of the incident deuteron energy and the12B recoil angle following the nuclear reaction. The nuclear magnetic moment of the short-lived nuclei12B was measured by β-NMR with the β-NMR and β-NQR setup established for the first time in China. The nuclear magnetic moment of12B was determined to be μ=0.99993±0.00048 nm org=0.99993±0.00048 after the precise correction of the Knight shift.  相似文献   
23.
Nagatomo  T.  Matsuta  K.  Hashimoto  K.  Ota  M.  Arimura  K.  Minamisono  K.  Sumikama  T.  Ogura  M.  Iwakoshi  T.  Miyake  T.  Kudo  S.  Akutsu  K.  Minamisono  T.  Fukuda  M.  Mihara  M.  Momota  S.  Nojiri  Y.  Kitagawa  A.  Torikoshi  M.  Kanazawa  M.  Suda  M.  Hirai  M.  Symons  T. J. M.  Krebs  G. F.  Alonso  J. R.  Zhu  S. Y.  Zhu  J. Z.  Xu  Y. J. 《Hyperfine Interactions》2001,136(3-8):233-237
The nuclear spin alignments of the β-emitting fragments 12B(I π=1+, T 1/2=20.2 ms) and 13B(I π=3/2, T 1/2=17.4 ms) produced in the 100A-MeV 13C, 15N + 9Be collisions respectively have been observed for the first time detecting asymmetric β-ray emission from these nuclei. By means of the spin manipulation technique based on the hyperfine interaction of B isotopes in TiO2, both the polarization P and the alignment A were determined reliably. The obtained P and A were significantly smaller than the expectation from the kinematical model. From the fact that the quenching factors for P and A are almost the same, there may be some depolarization mechanism in the collision process itself. This revised version was published online in September 2006 with corrections to the Cover Date.  相似文献   
24.
Shengyun  Zhu  Jiazheng  Zhu  Minamisono  T.  Matsuta  K.  Yongjun  Xu  Fukuda  M.  Mihara  M.  Zhiqiang  Wang  Sato  K.  Akai  H.  Chaofan  Rong  Chengjie  Chu  Jun  Chen  Hailong  Luo 《Hyperfine Interactions》2001,136(3-8):149-153
An on-line time differential perturbed angular correlation technique has been developed with the light probe nucleus 19F. The first on-line TDPAC measurement was carried out to determine the field gradient in Cd and quadrupole moment of 19F (0.197 MeV: I π = 5/2+, T1/2 = 89 ns). This revised version was published online in September 2006 with corrections to the Cover Date.  相似文献   
25.
The β-NMR study of short-lived nucleus 58Cu (I π ?=?1?+?, T 1/2?=?3.2 s) in Si has been performed. Spin polarization of 58Cu induced by the charge exchange reaction of 58Ni was observed in Si at 15 K. The 58Cu magnetic moment $|\upmu[^{58}\mbox{Cu}]| = (0.46 \pm 0.03)\upmu_{\rm N}$ deduced from the β-NMR spectrum is consistent with the previous results on the laser spectroscopy. The present result shows that the 58Cu nucleus is promising as a new nuclear probe for the microscopic study of Cu impurities in Si.  相似文献   
26.
Electric quadrupole coupling constant eqQ/h of the extremely proton-rich 23Al (I π ?=?5/2?+?, T 1/2?=?0.47 s) nucleus implanted into an Al2O3 single crystal has been measured for the first time, using the β-ray detecting nuclear quadrupole resonance method (β-NQR) in a high magnetic field. As a preliminary result, the quadrupole coupling constant was determined as |eqQ/h(23Al) |?=?2.66±0.77 MHz. Using the quadrupole coupling constant of 27Al in Al2O3 as a reference, the Q moment of the ground state of 23Al was extracted as |Q(23Al)|?~?160 mb, which is well explained by the shell model calculation in the sd-shell model space with the USD interaction.  相似文献   
27.
A 129Xe comagnetometer designed for the measurement of neutron electric dipole moment (nEDM) as precisely as 1 × 10?27e cm is presented. Highly nuclear spin polarized 129Xe are introduced into an EDM cell where the 129Xe spin precession is detected by means of the two-photon transition. The geometric phase effect (GPE) which generates the false nEDM was quantitatively discussed and the systematic error of nEDM from the GPE was estimated considering the buffer-gas suppression due to Xe atomic collisions. Research and development are in progress to construct the 129Xe comagnetometer with a field sensitivity of 0.3 fT. At present, about 70 % nuclear spin polarized 129Xe atoms have been obtained in a spin exchange opitial pumping cell, that are in the process of being transferred into the EDM cell via a cold trap.  相似文献   
28.
Fabrication of controlled peptide nanofibers with homogeneous morphology has been demonstrated. Amphiphilic beta-sheet peptides were designed as sequences of Pro-Lys-X(1)-Lys-X(2)-X(2)-Glu-X(1)-Glu-Pro. X(1) and X(2) were hydrophobic residues selected from Phe, Ile, Val, or Tyr. The peptide FI (X(1)=Phe; X(2)=Ile) self-assemble into straight fibers with 80-120 nm widths and clear edges, as examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The fiber formation is performed in a hierarchical manner: beta-sheet peptides form a protofibril, the protofibrils assemble side-by-side to form a ribbon, and the ribbons then coil in a left-handed fashion to make up a straight fiber. These type of fibers are formed from peptides possessing hydrophobic aromatic Phe residue(s). Furthermore, a peptide with Ala residues at both N and C termini does not form fibers (100 nm scale) with clear edges; this causes random aggregation of small pieces of fibers instead. Thus, the combination of unique amphiphilic sequences and terminal Pro residues determine the fiber morphology.  相似文献   
29.
A cholesteryl derived monomer was synthesized according to a conventional synthetic route; it exhibits a cholesteric phase above 129°C, and shows a red colour due to selective reflection in the cholesteric phase. Photopolymerization of the monomer was carried out at 135°C in the cholesteric phase. The helical structure of the cholesteric phase of the monomer was frozen by photopolymerization. A peak based on the selective reflection of the cholesteric phase was detected at 615 nm in the transmittance UV-Vis spectrum. Mixtures of the monomer with a binaphthyl derivative were prepared to control the selective reflection wavelength; they all also exhibited a cholesteric phase. The selective reflection wavelength of the mixture was dependent upon the ratio of the binaphthyl derivative in the mixture. This wavelength became shorter with increasing ratio of the binaphthyl derivative. The polymer films obtained by photopolymerization displayed almost the same selective reflection wavelength as the corresponding mixtures before photopolymerization. The selective reflection wavelength of the polymer films did not change up to about 250°C.  相似文献   
30.
The bicyclic amidines, 1,8‐diazabicyclo [5.4.0]undec‐7‐ene (DBU) and 1,5‐diazabicyclo[4.3.0] non‐5‐ene (DBN), were used for the chemical fixation of carbon dioxide. The promotion for CO2 fixation is often reported through the formation of a thermally unstable DBU or DBN bicarbonate salt. To examine the effects of the DBU or DBN bicarbonate salt, reactions of 2‐aminobenzonitrile with the DBU salt or DBN salt in dimethylformamide (DMF) were performed at 20°C for 24 h in argon or carbon dioxide (0.1 MPa). However, in all the cases, 1H‐quinazoline‐2,4‐dione was not obtained completely. In contrast with room temperature reactions, 2‐aminobenzonitriles and DBU bicarbonate salt in DMF reacted for 4 h under high temperature (80°C) and CO2 atmosphere (0.1 MPa) gave 1H‐quinazoline‐2,4‐diones in good to excellent yields. At high‐temperature conditions, DBU bicarbonate salt is decomposed to DBU and carbon dioxide. Also, the carbonylation of 2‐aminobenzonitrile using DBU and carbon dioxide afforded 1H‐quinazoline‐2,4‐dione in good yields under similar reaction conditions. These results suggest that the combination of DBU or DBN as a strong base and carbon dioxide is much more important than the in situ formation of DBU or DBN bicarbonate salt for the acceleration of CO2 fixation. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:276–280, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21014  相似文献   
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