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41.
Summary A new index of performance of the chromatographic separation between two adjacent peaks, the discrimination factor, d0, is defined. It is normalized between 0 and 1 and is directly and easily determined from the chromatogram. It does not depend
on any assumption regarding peak shape, except that the peak profiles of individual sample components have a single mode.
Its value depends on the relative heights of the two peaks as well as on their separation.
The separation power of a chromatographic system is classically measured by its peak capacity, defined on the basis of constant
resolution between adjacent peaks. A previously developed statistical theory of the composition of mixtures makes it possible
to extend the concept of peak capacity by taking into account the peak height distribution in typical average chromatograms.
A new parameter, the effective peak capacity, is defined for this purpose on the basis of a constant discrimination factor
between adjacent peaks. It allows to take into account the distribution of peak heights in statistical theories of the evaluation
of complex chromatograms and in the measurement of the limit of determination in quantitative analysis.
The characteristics of the two new parameters, the discrimination factor and effective peak capacity, are discussed and compared
with those of their classical homologs, resolution and peak capacity, in the case of gaussian component peaks of equal widths. 相似文献
42.
Zhaoyu Zhang Dr. Yufei Zhang Dr. Minghui Ye Dr. Zhipeng Wen Dr. Yongchao Tang Prof. Xiaoqing Liu Prof. Cheng Chao Li 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311032
The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+-conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm−2, presenting a record-high cumulative capacity up to 45 Ah cm−2. The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500 cycles). This work brings inspiration for developing fast-charging Zn batteries toward grid-scale storage of renewable energy sources. 相似文献
43.
Summary Herein is reported an analytical solution to the peak broadening or peak dispersion/flattening equation based on the recently proposed Instrumental Spreading Shape Function and its application to correction for imperfect resolution (inadequate peak separation and/or excessive peak broadening) for higher molecular weight averages. The relationship of these higher MW averages with the familiar Weight Average and number average molecular weights is also discussed. Criteria for perfect resolution are specified and a true molecular weight calibration curve is accordingly defined. 相似文献
44.
Hans-Georg Schmarr Birgit Maas Armin Mosandl Stephan Bihler Hans-Peter Neukom Konrad Grob 《Journal of separation science》1991,14(5):317-321
An unusual peak defocusing effect influencing chromatographic performance over a limited range of elution temperatures is described for hexakis(2,6-di-O-pentyl-3-O-acetyl)-α-cyclodextrin stationary phase. Since this phenomenon is likely to be dependent on minor details of the cyclodextrin molecule, full assignment of the 1H- and 13C-NMR-spectra are given. 相似文献
45.
Grand canonical ensemble approach to electrochemical thermodynamics,kinetics, and model Hamiltonians
The unique feature of electrochemistry is the ability to control reaction thermodynamics and kinetics by the application of electrode potential. Recently, theoretical methods and computational approaches within the grand canonical ensemble (GCE) have enabled to explicitly include and control the electrode potential in first principles calculations. In this review, recent advances and future promises of GCE density functional theory and rate theory are discussed. Particular focus is devoted to considering how the GCE methods either by themselves or combined with model Hamiltonians can be used to address intricate phenomena such as solvent/electrolyte effects and nuclear quantum effects to provide a detailed understanding of electrochemical reactions and interfaces. 相似文献
46.
Hong-Jing YU Wen-Wen XIA Li-Guo SONG Yang DING Yu HAO Li-Qiang KANG Xin-Xiang PAN Li YAO 《物理化学学报》2017,33(11):2207-2218
In this work, the harmonic and anharmonic rate constants of the decomposition reaction of monomethylhydrazine (MMH) radicals have been calculated by using transition state (TS) and Rice-Ramsperger-Kassel-Marcus (RRKM) theories with either MP2 or B3LYP method at 6-311++G (3df, 2p) basis set, respectively. The reaction mechanism and anharmonic effect of the MMH radicals are studied in detail and both of the harmonic and anharmonic rate constants increase sharply with increasing temperature in the canonical system. In the microcanonical system, these constants also show sharp increase with the energies. Overall, the anharmonic effect becomes more pronounced with the increasing temperature or energy in the canonical and microcanonical systems, respectively. These results indicate that the anharmonic effect of the decomposition reaction of MMH radicals is quite significant and cannot be ignored. 相似文献
47.
Omar S. Ahmed Michal Malý Yoann Ladner Laurent Philibert Pavel Dubský Catherine Perrin 《Electrophoresis》2019,40(21):2810-2819
A simple, sensitive, specific, and cost‐effective analytical methodology was developed for the analysis of human plasma samples spiked with imatinib by CZE with on‐line UV detection in the context of Therapeutic Drug Monitoring. Several analytical conditions such as the ionic strength (I) and the pH of the BGE composed of citric acid and ε‐amino caproic acid were studied in regards of the presence of sodium chloride (NaCl) in plasma samples (1% m/v). Computer simulations (Simul software) were used to confirm the experimental results and to understand imatinib electrophoretic behavior in the presence of NaCl. Furthermore, the advantages of adding ACN to the sample containing NaCl to combine efficient protein precipitation and on‐line CZE stacking of imatinib were demonstrated. LOD and LOQ values of 48 and 191 ng/mL were obtained from plasma sample supernatant after protein precipitation with ACN, which is much lower than mean imatinib plasma level observed for patients treated by imatinib mesylate (about 1000 ng/mL). Good linearity was obtained in the concentration range 191–5000 ng/mL (R2 > 0.997). RSD of less than 1.68% and 2.60% (n = 6) for migration times and corrected peak areas, respectively, were observed at the LOQ. 相似文献
48.
Rate Coeffcients and Branching Ratio for Multi-Channel Hydrogen Abstractions from CH3OH by F 下载免费PDF全文
The hydrogen abstraction reaction F+CH3OH has two possible reaction pathways: HF+CH3O and HF+CH2OH. Despite the absence of intrinsic barriers for both channels, the former has a branching ratio comparable to the latter, which is far from the statistical limit of 0.25 (one out of four available H atoms). Furthermore, the measured branching ratio of the two abstraction channels spans a large range and is not quantitatively reproduced by previous theoretical predictions based on the transition-state theory with the stationary point information calculated at the levels of M?ller-Plesset perturbation theory and G2. This work reports a theoretical investigation on the kinetics and the associated branching ratio of the two competing channels of the title reaction using a quasi-classical trajectory approach on an accurate full-dimensional potential energy surface (PES) fitted by the permutation invariant polynomial-neural network approach to ca. 1.21x105 points calculated at the explicitly correlated (F12a) version of coupled cluster singles doubles and perturbative triples (CCSD(T)) level with the aug-cc-pVDZ basis set. The calculated room temperature rate coeffcient and branching ratio of the HF+CH3O channel are in good agreement with the available experimental data. Furthermore, our theory predicts that rate coeffcients have a slightly negative temperature dependence, consistent with barrierless nature of the reaction. 相似文献
49.
D. Husain J. Lei F. Castao M. N. Snchez Rayo 《Journal of photochemistry and photobiology. A, Chemistry》1999,120(3):151-159
The collisional behaviour of Ba[6s5d(3DJ)], 1.151 eV above the 6s2(1S0) electronic ground state, in the presence of atomic strontium, has been investigated in the ‘long-time domain' (ca. 100 μs–1 ms) following the pulsed dye-laser excitation of barium vapour at elevated temperature at λ = 553.5 nm (Ba[6s6p(1P1)] ← Ba[6s2(1S0)]. Ba(3DJ) is subsequently produced from the short-lived 1P1 state (τe = 8.37 ± 0.38 ns) by a number of radiative and collisional processes. It may then be monitored in the ‘long-time domain' by atomic spectroscopic marker methods involving either collisional activation of Ba(3DJ) by Ba(1S0) and He buffer gas to yield Ba[6s6p(3PJ)] with subsequent emission from the 3P1 state (τe = 1.2 ± 0.1 μs): Ba[6s6p(3P1)] → Ba[6s2(1S0)] + hv (λ = 791.1 nm). Alternatively, emission from Ba(1P1) may be monitored at long times following the generation of this short-lived state by energy pooling following self-annihilation of Ba(3DJ) + Ba(3DJ) from Ba[6s6p(1P1)] → Ba[6s2(1S0)] + hv (λ = 553.5 nm). The generation of Ba(3DJ) in the presence of atomic strontium yields emission in the long-time domain from Sr[5s5p(3P1)] (τe = 19.6 μs): Sr[5s5p(3P1)] → Sr[5s2(1S0)] + hv (λ = 689.3 nm). Whilst the decay profiles at short times are complex in form, at long times all these atomic profiles show first-order kinetic removal with the decay coefficients for λ = 791.1 nm, 689.3 nm and 553.5 nm emissions in the ratio 1 : 2 : 2, consistent with overall third-order activation of the form: Ba(3DJ) + Ba(3DJ) + Sr(1S0) → Sr(3PJ) + 2Ba(1S0). The mechanism is modelled in detail, including measurement of integrated emission intensities, yielding kinetic data for fundamental collisional processes. The overall rate constant for the third-order collisional activation of Sr[5s5p(3PJ])from 2Ba[6s5d(3DJ)] + Sr[5s2(1S0)] takes the upper limit of 5.8 × 10−27 cm6 atom−2 s−1 (T = 900 K). The rate constant for the two body collisional quenching of Ba[6s5d(3DJ)] by ground state atomic strontium, Sr[5s2(1S0)], is found to be (2.0 ± 0.1) × 10−12 cm3 atom−1 s−1 (T = 900 K). 相似文献
50.
龚健 《高等学校化学学报》1990,11(9):1025-1027
TPD技术[1]已成为研究固体表面性质的重要手段,本文在总结前人工作的基础上考察了TPD谱峰峰宽和相应参数与脱附活化能(Ed)之间的变化规律,证明用任意峰宽法或半峰宽法测定Ed值有很好的实用性,该法直接运用TPD谱图参数,无需另外作图,故十分快速、简便,与其它方法比较,结果吻合。 相似文献