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41.
Belik AA Azuma M Matsuo A Whangbo MH Koo HJ Kikuchi J Kaji T Okubo S Ohta H Kindo K Takano M 《Inorganic chemistry》2005,44(19):6632-6640
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy. 相似文献
42.
Low-spin ferric porphyrin radical cations formed by the oxidation of chloro(meso-tetraalkylporphyrinato)iron(III) followed by the addition of bulky 2-methylimidazole show antiferromagnetic coupling, which is interpreted in terms of the interaction between porphyrin a2u and iron d(xy), orbitals caused by the S4 ruffling of the porphyrin core. 相似文献
43.
Anyun Zhang Yuezhou Wei Harutaka Hoshi Mikio Kumagai Masayoshi Kamiya Tomozo Koyama 《Radiation Physics and Chemistry》2005,72(6):669-678
The resistance of a novel silica-based N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption material (TODGA/SiO2-P) against nitric acid, temperature and γ-irradiation had been investigated. The adsorption property of the treated TODGA/SiO2-P was evaluated by a 3 M HNO3 solution containing 0.01 M Nd(III). It was found that both 3 and 0.01 M HNO3 concentrations did not decrease the stability of TODGA/SiO2-P at 25°C. The quantity of TODGA leaked from TODGA/SiO2-P was equivalent to its solubility in the corresponding HNO3 aqueous solution. The effect of 3 M HNO3 on the leakage of TODGA at 80°C was significantly higher than that in 0.01 M HNO3 as well as in all cases at 25°C. The amount of Nd(III) adsorbed towards the treated TODGA/SiO2-P was determined in the range of 0.143–0.148 mmol/g for the HNO3 concentration effect and 0.142–0.0506 mmol/g for the temperature effect. γ-Irradiation showed a more noticeable destruction effect on TODGA/SiO2-P. The content of TODGA leaked increased with an increase in the γ-irradiation dose (ID) from 1.06 to 3.72 MGy in terms of the linear equation [TODGA]=794.5ID+84.0. The amount of Nd(III) adsorbed onto the irradiated TODGA/SiO2-P decreased rapidly from 0.134 to 0.0438 mmol/g, which was lower than 0.153 mmol/g, the adsorption of fresh TODGA/SiO2-P for Nd(III), according to the equation QNd(III)=−0.0301ID+0.160, showing that a large quantity of TODGA leaked from TODGA/SiO2-P. The adsorbed amount of Nd(III) decreased obviously in this order: the HNO3 concentration effect, temperature effect and γ-irradiation. 相似文献
44.
Shoichi Katsuta Tokutaro Kimura Yoshihiro Kudo Ryozo Nakagawa Yasuyuki Takeda Mikio Ouchi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(2):89-98
The overall extraction constants (Kex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheKex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The Kex valuedecreases in the orders Ag+ > Na+ >Tl+ > K+ > Li+ andPb2+ > Ba2+ > Sr2+ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant. 相似文献
45.
The electronic states of a series of saddle-shaped porphyrin complexes [Fe(OMTPP)L(2)](+) and [Fe(TBTXP)L(2)](+) have been examined in solution by (1)H NMR, (13)C NMR, and EPR spectroscopy and by magnetic measurements. While [Fe(OMTPP)(DMAP)(2)](+) and [Fe(TBTXP)(DMAP)(2)](+) maintain the low-spin (S = (1)/(2)) state, [Fe(OMTPP)(THF)(2)](+) and [Fe(TBTXP)(THF)(2)](+) exhibit an essentially pure intermediate-spin (S = (3)/(2)) state over a wide range of temperatures. In contrast, the Py and 4-CNPy complexes of OMTPP and TBTXP exhibit a spin transition from S = (3)/(2) to S = (1)/(2) as the temperature was decreased from 300 to 200 K. Thus, the magnetic behavior of these complexes is similar to that of [Fe(OETPP)Py(2)](+) reported in our previous paper (Ikeue, T.; Ohgo, Y.; Yamaguchi, T.; Takahashi, M.; Takeda, M.; Nakamura, M. Angew. Chem., Int. Ed. 2001, 40, 2617-2620) in the context that all these complexes exhibit a novel spin crossover phenomenon in solution. Close examination of the NMR and EPR data of [Fe(OMTPP)L(2)](+) and [Fe(TBTXP)L(2)](+) (L = Py, 4-CNPy) revealed, however, that these complexes adopt the less common (d(xz), d(yz))(4)(d(xy))(1) electron configuration at low temperature in contrast to [Fe(OETPP)Py(2)](+) which shows the common (d(xy))(2)(d(xz), d(yz))(3) electron configuration. These observations have been attributed to the flexible nature of the OMTPP and TBTXP cores as compared with that of OETPP; the relatively flexible OMTPP and TBTXP cores can ruffle the porphyrin ring and adopt the (d(xz), d(yz))(4)(d(xy))(1) electron configuration at low temperature. Therefore, this study reveals that the rigidity of porphyrin cores is an important factor in determining the spin crossover pathways. 相似文献
46.
Hironori Tohmyoh Shoho Ishikawa Mikio Muraoka 《Surface and interface analysis : SIA》2012,44(9):1294-1298
An eddy current microscopy technique to evaluate the electrical conductivity of thin metallic films in a non‐contact manner is reported. A narrow track formed in an approximately 100 nm thick Au film was prepared, and a Co–Cr coated magnetic tip was driven to oscillate above the track both with and without current passing through the track. Despite the absence of current, the electromagnetic interaction between the tip and the stray magnetic field from the track gave rise to a phase delay in the probe. This was due to an eddy current being induced within part of the track. Moreover, measurements of the phase change in the probe oscillation for different metallic films with thicknesses of about 100 nm found this to be proportional to the electrical conductivity of the film. Finally, the electrical conductivity of an Al film was evaluated using the eddy current microscopy technique. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
47.
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49.
Manabu Ishifune Ryuhei Suzuki Mikio Yamane Hiroyuki Tanabe Yuki Nakagawa Kumao Uchida 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):523-528
Acrylamide (AAm) was found to polymerize in a solution of poly(N‐isopropylacrylamide) (PNIPAAm) in water at around its lower critical solution temperature (LCST) (32°C) without any initiators. This phenomenon was specifically observed in aqueous solutions of the polymers having LCST such as PNIPAAm and poly(methylvinylether) (PMVE). AAm polymerized only when PNIPAAm and AAm were dissolved in water below LCST of PNIPAAm and then the solution was warmed up to the polymerization temperature (40°C). On the other hand, the polymerization of AAm did not proceed when AAm was added into aqueous PNIPAAm solution during and after the phase separation above 32°C. Furthermore the polymerizability of AAm was remarkably affected by the concentration and molecular weight of the PNIPAAm additives. Under the condition of lower PNIPAAm concentration (0.30 mol/L), the increase in the molecular weight of PNIPAAm considerably increased the molecular weight of the resulting PAAm but decreased the yield of PAAm. Under the condition of higher PNIPAAm concentration (0.60 mol/L) the polymerizability was not so affected by the molecular weight of PNIPAAm, while the molecular weight of PAAm formed by using higher molecular weight PNIPAAm was higher than those of PAAm formed by using lower molecular weight PNIPAAm. Moreover, the molecular weight of PAAm formed by the PNIPAAm induced polymerization of AAm was much higher than that of the polymer obtained by the radical polymerization using AIBN in THF or VA‐ 061 in water. 相似文献
50.
Abstract Calorimetric titrations have been performed in anhydrous acetonitrile at 25°C to give the complex stability constants (K s) and the thermodynamic parameters (ΔGΔ, ΔHΔ and ΔSΔ) for the complexation of light lanthanoid(III) nitrates (La-Gd) with N-benzylaza-21-crown-7 3. Data analyses, assuming 1:1 stoichiometry, were successfully applied to all light lanthanoid-azacrown ether combinations employed. Using the present and previous data on 15- to 21- membered N-benzylazacrown ethers 1–3, the effect of ring size upon complexation behavior was discussed comparatively and globally from the thermodynamic point of view. The complexation behaviors are analyzed in terms of the size-fit concept, N-substituent coordination numbers, and lanthanoid's surface charge density. Thermodynamically the complexation of light lanthanoids with azacrown ethers is enthalpy-driven, while the cation selectivity is generally entropy-driven in acetonitrile. 相似文献