全文获取类型
收费全文 | 2444篇 |
免费 | 115篇 |
国内免费 | 16篇 |
专业分类
化学 | 1893篇 |
晶体学 | 13篇 |
力学 | 34篇 |
综合类 | 16篇 |
数学 | 232篇 |
物理学 | 387篇 |
出版年
2023年 | 20篇 |
2022年 | 19篇 |
2021年 | 39篇 |
2020年 | 49篇 |
2019年 | 57篇 |
2018年 | 38篇 |
2017年 | 26篇 |
2016年 | 60篇 |
2015年 | 50篇 |
2014年 | 59篇 |
2013年 | 131篇 |
2012年 | 158篇 |
2011年 | 162篇 |
2010年 | 81篇 |
2009年 | 102篇 |
2008年 | 178篇 |
2007年 | 155篇 |
2006年 | 139篇 |
2005年 | 151篇 |
2004年 | 129篇 |
2003年 | 102篇 |
2002年 | 104篇 |
2001年 | 38篇 |
2000年 | 41篇 |
1999年 | 27篇 |
1998年 | 28篇 |
1997年 | 42篇 |
1996年 | 36篇 |
1995年 | 19篇 |
1994年 | 20篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 13篇 |
1990年 | 23篇 |
1989年 | 14篇 |
1988年 | 18篇 |
1987年 | 13篇 |
1986年 | 11篇 |
1985年 | 21篇 |
1984年 | 18篇 |
1983年 | 15篇 |
1982年 | 23篇 |
1981年 | 22篇 |
1980年 | 17篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 12篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 10篇 |
排序方式: 共有2575条查询结果,搜索用时 15 毫秒
71.
The annulenium ions of protonation, the two-electron oxidation dications, and the two-electron reduction dianions derived from dihydro- and dimethyldihydro derivatives (cis and trans) of dicyclopenta[ef,kl]heptalene (azupyrene) (1) and dicyclohepta[ed,gh]pentalene (2), which are the nonalternant isomers of pyrene, were studied by density functional theory (DFT) at the B3LYP/6-31G(d), 6-31+G(d,p), or 6-31++G(d,p) levels. Charge delocalization modes in the energetically most favored annulenium ions, as well as in the singlet and triplet dications and dianions, were assessed based on gauge-including atomic orbital (GIAO) Deltadelta](13)C values and via changes in natural population analysis (NPA) charges. Relative aromaticity/antiaromaticity in the annulenes were gauged via nucleus-independent chemical shift (NICS) and DeltaNICS. Annulenium ions of monoprotonation, the dications, and dianions derived from bismethano- and propanediylidene [14]annulenes were also studied by DFT for comparison with the cis-dihydro isomers derived from . Computed GIAO NMR data and the optimized geometries were compared with the experimental data when available, and the optimized geometries were compared with the X-ray data if known. A basis-set dependency study of the computed GIAO chemical shifts was also undertaken. The present DFT work represents the first detailed comparative theoretical study of charged annulenes derived from the dihydro derivatives of and . 相似文献
72.
A simple and automated methodology for a sensitive electrochemical detection of enzyme immunoassays that employ alkaline phosphatase (AP) as label has been developed. A flow injection system with programmable pump, valve and cell functions, amperometric detection of indigo and screen-printed electrodes (SPEs) are responsible for the advantages of this methodology. Amperometric detection at a low potential of indigo, the product of the enzymatic hydrolysis of the substrate 3-indoxyl phosphate (IP), is combined with a flow injection system. This incorporates in the flow cell a disposable screen-printed board provided with a graphite working electrode. No electrode pretreatment is necessary to obtain reproducible signals. The system was applied to the determination by an enzyme-linked immunosorbent assays (ELISA) of pneumolysin (PLY), a toxin related to respiratory infections. Linear calibration curves for low and high concentration ranges were obtained. These were also performed in a proteic matrix and linearity was also obtained. 相似文献
73.
The Grignard coupling of 2,2-dibromo-1-phenyladamantane gave trans-2,2'-bi(1-phenyladamantylidene) (1-Ph). Single-crystal X-ray analysis indicated that 1-Ph has a 23.2 degrees twisted double bond, which is much more distorted than that of parent 2,2'-biadamantylidene (1-H) and that of the ethyl-substituted derivative (1-Et). A cyclic voltammogram showed a reversible electron oxidation wave at 0.87 V vs Fc/Fc(+), which is 0.19 V lower than 1-H, indicating a significant increase in the HOMO energy level due to the distortion. The reaction of 1-Ph with 0.9 equiv of bromine gave an intramolecular Friedel-Crafts alkylation product, while bromination of 1-H and 1-Me has been reported to give a bridged bromonium ion and a rearranged product, 2-(1-methyl-2-adamantylidene)-4-bromotricyclo[5,3,1,0(3.9)]undec-4-ene, respectively. 相似文献
74.
The structural characteristics of methanol in aqueous solutions, on a molecular level, can be elucidated by four types of calculation: molecular orbital, multiparametric optimization of intermolecular potential function, Monte Carlo, and molecular dynamics. As a first step, the potential between water and methanol was determined by ab initio LCAO SCF molecular orbital calculations with the STO—3G basis set and subsequent multiparametric fitting. This and water—water potentials were used for Monte Carlo calculation on an aqueous methanol solution containing a 1:216 mole ratio of methanol to water. Hydration around methanol is briefly discussed. 相似文献
75.
The assembly strategy to prepare a monolayer of bovine serum albumin on the surface of silica gel supported gold nanoparticles is described. The stereo‐specific recognition ability of this material was evaluated by enantioresolution of Dansyl‐norvaline. For enantiomeric separation, the influences of buffer concentration and the concentration of organic modifier on the separation performance were investigated. A better separation in terms of enantioresolution and peak shape was found with the phosphate concentration at 30 mM. Moreover, the peak shape and resolution can be improved by the addition of methanol solution. Enantioresolution of Dansyl‐norvaline was obtained from this material at optimized conditions. It appears that the immobilization of a monolayer of bovine serum albumin on gold nanoparticles as the chiral selector of Dansyl‐derivative amino acid is promising. 相似文献
76.
The standardization of EDTA solution against metallic copper as primary standard is studied. Six indicators were examined; titration with PAN as indicator at pH 6 is recommended. 相似文献
77.
Turowski M Yamakawa N Meller J Kimata K Ikegami T Hosoya K Tanaka N Thornton ER 《Journal of the American Chemical Society》2003,125(45):13836-13849
Hydrogen/deuterium isotope effects on hydrophobic binding were examined by means of reversed-phase chromatographic separation of protiated and deuterated isotopologue pairs for a set of 10 nonpolar and low-polarity compounds with 10 stationary phases having alkyl and aryl groups bonded to the silica surface. It was found that protiated compounds bind to nonpolar moieties attached to silica more strongly than deuterated ones, demonstrating that the CH/CD bonds of the solutes are weakened or have less restricted motions when bound in the stationary phase compared with the aqueous solvent (mobile phase). The interactions responsible for binding have been further characterized by studies of the effects of changes in mobile phase composition, temperature dependence of binding, and QSRR (quantitative structure-chromatographic retention relationship) analysis, demonstrating the importance of enthalpic effects in binding and differentiation between the isotopologues. To explain our results showing the active role of the hydrophobic (stationary) phase we propose a plausible model that includes specific contributions from aromatic edge-to-face attractive interactions and attractive interactions of aliphatic groups with the pi clouds of aromatic groups present as the solute or in the stationary phase. 相似文献
78.
High-performance liquid chromatographic determination of (S)-(-)-ofloxacin and its metabolites in serum and urine using a solid-phase clean-up 总被引:3,自引:0,他引:3
A sensitive and selective method for the simultaneous determination of (S)-(-)-ofloxacin [(S)-(-)-OFLX] and its metabolites in serum and urine was developed using isocratic high-performance liquid chromatography with a specific solid-phase extraction procedure. (S)-(-)-OFLX and its metabolites, desmethyl-(S)-(-)-OFLX and (S)-(-)-OFLX N-oxide, were eluted from a C8 solid-phase column with recoveries of more than 98%. These compounds were separated and determined by means of a reversed-phase column with fluorimetric detection. Validation studies showed that the results were linear for (S)-(-)-OFLX in serum over the range 10-1200 ng/ml and in urine over the range 1-200 micrograms/ml. Analysis for (S)-(-)-OFLX and its metabolites showed good precision and accuracy with a relative standard deviation of less than 6%. 相似文献
79.
We measured FT-IR spectra of intact Acholeplasma laidlawii cells grown at 37 °C on palmitic acid (C16:0) or on binary palmitic acid-d31/oleic acid (C16:0-d31/C18:1(9)) at an initial mole ratio of 2:3, which have been previously reported to produce significant fluctuations in CH2 symmetric stretching (νsCH2) and CD2 asymmetric stretching (νaCD2) frequencies (Biochim. Biophys. Acta 1279 (1996) 49). Time courses for acyl chain νsCH2 and νaCD2 frequencies determined from fourth derivative spectra are presented. Fluctuations were detected with the C16:0 enriched cells at temperatures above 40 °C as well as with the cells enriched in 2:3 C16:0-d31/C18:1(9). These observations at temperatures above 40 °C for the C16:0 enriched cells were not in agreement with the conclusion in the previous work by Moore et al. Our results have suggested that the 2850 cm−1 νsCH2 band comprises two components arising from trans and gauche conformations, and that the fluctuations in νsCH2 frequency are caused by random temporal changes in the relative intensities of these two components. 相似文献
80.
Motokawa M Kobayashi H Ishizuka N Minakuchi H Nakanishi K Jinnai H Hosoya K Ikegami T Tanaka N 《Journal of chromatography. A》2002,961(1):53-63
Reduction of through-pore size and skeleton size of a monolithic silica column was attempted to provide high separation efficiency in a short time. Monolithic silica columns were prepared to have various sizes of skeletons (approximately 1-2 microm) and through-pores (approximately 2-8 microm) in a fused-silica capillary (50-200 microm I.D.). The columns were evaluated in HPLC after derivatization to C18 phase. It was possible to prepare monolithic silica structures in capillaries of up to 200 microm I.D. from a mixture of tetramethoxysilane and methyltrimethoxysilane. As expected, a monolithic silica column with smaller domain size showed higher column efficiency and higher pressure drop. High external porosity (> 80%) and large through-pores resulted in high permeability (K = 8 x 10(-14) -1.3 x 10(-12) m2) that was 2-30 times higher than that of a column packed with 5-mirom silica particles. The monolithic silica columns prepared in capillaries produced a plate height of about 8-12 microm with an 80% aqueous acetonitrile mobile phase at a linear velocity of 1 mm/s. Separation impedance, E, was found to be as low as 100 under optimum conditions, a value about an order of magnitude lower than reported for conventional columns packed with 5-microm particles. Although a column with smaller domain size generally resulted in higher separation impedance and the lower total performance, the monolithic silica columns showed performance beyond the limit of conventional particle-packed columns under pressure-driven conditions. 相似文献