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991.
Some new experimental methods for measuring the optical chirality of molecular aggregates formed at liquid–liquid interfaces
have been reviewed. Chirality measurements of interfacial aggregates are highly important not only in analytical spectroscopy
but also in biochemistry and surface nanochemistry. Among these methods, a centrifugal liquid membrane method was shown to
be a highly versatile method for measuring the optical chirality of the liquid–liquid interface when used in combination with
a commercially available circular dichroism (CD) spectropolarimeter, provided that the interfacial aggregate exhibited a large
molar absorptivity. Therefore, porphyrin and phthalocyanine were used as chromophoric probes of the chirality of itself or
guest molecules at the interface. A microscopic CD method was also demonstrated for the measurement of a small region of a
film or a sheet sample. In addition, second-harmonic generation and Raman scattering methods were reviewed as promising methods
for detecting interfacial optical molecules and measuring bond distortions of chiral molecules, respectively. 相似文献
992.
Enhancement of peroxyoxalate chemiluminescence (PO-CL) intensity by a surfactant in the H2O2/bis(2,4,6-trichlorophenyl)oxalate (TCPO)/rhodamine B system was described. The effects of 15 surfactants were evaluated by comparing the ratio of a relative CL intensity (RCI) with surfactant to that of the blank in each system. In preliminary study, H2O2/imidazole-HNO3 buffer/TCPO/rhodamine B system was used to study the effects of surfactants on PO-CL intensity. Fourteen surfactants reduced the CL intensity at the 2% concentration, where their relative CL intensities ranged from 0.6 to 93.5%. Some of these phenomena may be caused by a notable change of pH that was occurred by adding the surfactant.Additionally, enhancement of PO-CL intensity was studied by using system (1) H2O2/TCPO/rhodamine B and (2) H2O2/imidazole-HNO3 buffer/TCPO/systems. In the system 1, the favorable enhancement of CL intensity (ranged from 124 to 472%) was observed with 9 surfactants at the 0.5% concentration. This result suggested that several surfactants might play a role as a catalyst in the PO-CL reaction. There was no tendency to enhance CL intensity among the surfactant types. In the system 2, the enhancement of CL intensity was also observed by adding with 11 surfactants, which might be mainly caused by the fluorescent impurities of surfactants used.Furthermore, detection of detergent commercially available was applied by using the system 1. 相似文献
993.
The first example of a new Hg(2+)-sensing system based on the structures of complexes is reported. The system uses a combination of a new chiral bidentate ligand and CD spectroscopy. Significant CD spectral changes are observed when Hg(2+) is added, whereas no CD spectral changes are observed in the cases of Li(+), Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Rb(+), Ag(+), Cd(2+), La(3+), Gd(3+), and Pb(2+). 相似文献
994.
Y Habata M Ikeda S Yamada H Takahashi S Ueno T Suzuki S Kuwahara 《Organic letters》2012,14(17):4576-4579
Tetra-armed cyclens bearing aromatic side arms were prepared by the reductive amination of cyclen with substituted benzaldehydes. When equimolar amounts of Ag(+) ions were added to the ligands, the aromatic rings covered the Ag(+) ions incorporated in the ligand cavities, as if the aromatic ring "petals" caught the Ag(+) ions in the way an insectivorous plant (Venus flytrap) catches insects. The ligands are called "argentivorous molecules". Evidence of intramolecular Ag(+)-π interactions in solution and in the solid state is reported. 相似文献
995.
A novel palladium- and copper-catalyzed one-pot multicomponent synthesis of hetero α,α'-dimers of heterocycles via Sonogashira coupling and double cyclization cascade involving imine formation has been developed. This reaction cascade proceeded under mild conditions, providing a powerful synthetic tool for the assembly of π-conjugated systems with a combination of palladium-catalyzed post-direct C-H bond arylations. 相似文献
996.
Wada M Ochi Y Nogami K Ikeda R Kuroda N Nakashima K 《Analytical and bioanalytical chemistry》2012,403(9):2569-2576
We describe the use of hair roots as a matrix for detection of methamphetamine (MP) and 3,4-methylenedioxymethamphetamine (MDMA) abuse. The concentration of drugs was determined in rat hair roots, hair shafts, and plasma after a single administration of MP or MDMA, by use of an HPLC-peroxyoxalate chemiluminescence (PO-CL) method involving column switching. Plasma and hair roots and shafts were collected from male Wistar rats before and after administration of MP (10 mg kg(-1), i.p.). In addition, the roots and shafts of pigmented and non-pigmented hair of male Lister hooded rats were collected after administration of MDMA (10 mg kg(-1), i.p.). The concentrations of MP and MDMA in plasma and hair were determined by use of the HPLC-PO-CL method, with satisfactory sensitivity and reproducibility. The concentration of MP in hair roots 1-14 days after administration ranged from 0.038 to 0.115 ng mg(-1) (n = 3). By use of the HPLC-PO-CL method, MP could be detected in hair roots for longer (up to 14 days) than it could be detected in conventional biological specimens, for example plasma (~1 day), and MDMA was detected in hair roots from 1 to 10 days after administration. The AUC(1-10) (ng day mg(-1)) for MDMA in roots of non-pigmented and pigmented hair was comparable (4.93 ± 2.09 vs. 6.67 ± 1.28, n = 3), whereas AUC(1-14) for hair shafts differed significantly (1.86 ± 0.93 vs. 4.58 ± 0.63, P < 0.05, n = 3). The window for detecting MP (or MDMA) in hair roots under our conditions was 1-14 (or 1-10) days. 相似文献
997.
Akio Toyoshima Takashi Kikuchi Hirokazu Tanaka Jun‐ichi Adachi Kazuhiko Mase Kenta Amemiya 《Journal of synchrotron radiation》2012,19(5):722-727
Carbon contamination of optics is a serious issue in all soft X‐ray beamlines because it decreases the quality of experimental data, such as near‐edge X‐ray absorption fine structure, resonant photoemission and resonant soft X‐ray emission spectra in the carbon K‐edge region. Here an in situ method involving the use of oxygen activated by zeroth‐order synchrotron radiation was used to clean the optics in a vacuum ultraviolet and soft X‐ray undulator beamline, BL‐13A at the Photon Factory in Tsukuba, Japan. The carbon contamination of the optics was removed by exposing them to oxygen at a pressure of 10?1–10?4 Pa for 17–20 h and simultaneously irradiating them with zeroth‐order synchrotron radiation. After the cleaning, the decrease in the photon intensity in the carbon K‐edge region reduced to 2–5%. The base pressure of the beamline recovered to 10?7–10?8 Pa in one day without baking. The beamline can be used without additional commissioning. 相似文献
998.
Ikeda T Sakota K Kawashima Y Shimazaki Y Sekiya H 《The journal of physical chemistry. A》2012,116(15):3816-3823
Photoionization-induced water migration in the trans-formanilide-water 1:1 cluster, FA-(H(2)O)(1), has been investigated by using IR-dip spectroscopy, quantum chemical calculations, and ab initio molecular dynamics simulations. In the S(0) state, FA-(H(2)O)(1) has two structural isomers, FA(NH)-(H(2)O)(1) and FA(CO)-(H(2)O)(1), where a water molecule is hydrogen-bonded (H-bonded) to the NH group and the CO group, respectively. In addition, the S(1)-S(0) origin transition of FA(CO)-(H(2)O)(2), where a water dimer is H-bonded to the CO group, was observed only in the [FA-(H(2)O)(1)](+) mass channel, indicating that one of the water molecules evaporates completely in the D(0) state. These results are consistent with a previous report [Robertson, E. G. Chem. Phys. Lett., 2000, 325, 299]. In the D(0) state, however, [FA-(H(2)O)(1)](+) produced by photoionization via the S(1)-S(0) origin transitions of FA(NH)-(H(2)O)(1) and FA(CO)-(H(2)O)(1) shows essentially the same IR spectra. Compared with the theoretical calculations, [FA-(H(2)O)(1)](+) can be assigned to [FA(NH)-(H(2)O)(1)](+). This means that the water molecule in [FA-(H(2)O)(1)](+) migrates from the CO group to the NH group when [FA-(H(2)O)(1)](+) is produced by photoionization of FA(CO)-(H(2)O)(1). [FA-(H(2)O)(1)](+) produced by photoionization of FA(CO)-(H(2)O)(2) also shows the IR spectrum corresponding to [FA(NH)-(H(2)O)(1)](+). In this case, the water migration from the CO group to the NH group occurs with the evaporation of a water molecule. Ab initio molecular dynamics simulations revealed the water migration pathway in [FA-(H(2)O)(1)](+). The calculations of classical electrostatic interactions show that charge-dipole interaction between FA(+) and H(2)O induces an initial structural change in [FA-(H(2)O)(1)](+). An exchange repulsion between the lone pairs of the CO group and H(2)O in [FA-(H(2)O)(1)](+) also affects the initial direction of the water migration. These two factors play important roles in determining the initial water migration pathway. 相似文献
999.
H. S. Yamada K. S. Ikeda 《The European Physical Journal B - Condensed Matter and Complex Systems》2012,85(1):41
This paper concerns the time-reversal characteristics of intrinsic normal diffusion in quantum systems. Time-reversible properties
are quantified by the time-reversal test; the system evolved in the forward direction for a certain period is time-reversed
for the same period after applying a small perturbation at the reversal time, and the separation between the time-reversed
perturbed and unperturbed states is measured as a function of perturbation strength, which characterizes sensitivity of the
time reversed system to the perturbation and is called the time-reversal characteristic. Time-reversal characteristics are
investigated for various quantum systems, namely, classically chaotic quantum systems and disordered systems including various
stochastic diffusion system. When the system is normally diffusive, there exists a fundamental quantum unit of perturbation,
and all the models exhibit a universal scaling behavior in the time-reversal dynamics as well as in the time-reversal characteristics,
which leads us to a basic understanding of the nature of quantum irreversibility. 相似文献
1000.
Satoshi Tohoda Daisuke Fujishima Ayumu Yano Akiyoshi Ogane Kenta Matsuyama Yuya Nakamura Nozomu Tokuoka Hiroshi Kanno Toshihiro Kinoshita Hitoshi Sakata Mikio Taguchi Eiji Maruyama 《Journal of Non》2012,358(17):2219-2222
To reduce the power generation cost of heterojunction with intrinsic thin layer (HIT) solar cells, it is necessary to use a thinner crystalline silicon wafer, as well as to improve the conversion efficiency. We have experimentally confirmed that VOC of the HIT solar cell increases with decreasing the wafer thickness, and can reach a very high VOC of 747 mV with a 58-μm-thick wafer owing to a sufficiently low surface recombination velocity. We also indicate the future directions for improving the efficiency. The uniformization of the texture size of the silicon surface and reduction of the carrier density in TCO film while maintaining an equal or lower conductivity are effective for improving the optical confinement. 相似文献