全文获取类型
收费全文 | 34298篇 |
免费 | 1684篇 |
国内免费 | 2194篇 |
专业分类
化学 | 33883篇 |
晶体学 | 406篇 |
力学 | 690篇 |
综合类 | 136篇 |
数学 | 151篇 |
物理学 | 2910篇 |
出版年
2024年 | 27篇 |
2023年 | 310篇 |
2022年 | 654篇 |
2021年 | 515篇 |
2020年 | 787篇 |
2019年 | 820篇 |
2018年 | 894篇 |
2017年 | 1208篇 |
2016年 | 1450篇 |
2015年 | 1187篇 |
2014年 | 1134篇 |
2013年 | 2645篇 |
2012年 | 2108篇 |
2011年 | 1843篇 |
2010年 | 1640篇 |
2009年 | 1975篇 |
2008年 | 1498篇 |
2007年 | 1723篇 |
2006年 | 1524篇 |
2005年 | 1420篇 |
2004年 | 1221篇 |
2003年 | 991篇 |
2002年 | 869篇 |
2001年 | 736篇 |
2000年 | 786篇 |
1999年 | 746篇 |
1998年 | 658篇 |
1997年 | 644篇 |
1996年 | 604篇 |
1995年 | 635篇 |
1994年 | 526篇 |
1993年 | 436篇 |
1992年 | 332篇 |
1991年 | 371篇 |
1990年 | 330篇 |
1989年 | 305篇 |
1988年 | 395篇 |
1987年 | 381篇 |
1986年 | 297篇 |
1985年 | 281篇 |
1984年 | 299篇 |
1983年 | 149篇 |
1982年 | 263篇 |
1981年 | 194篇 |
1980年 | 161篇 |
1979年 | 150篇 |
1978年 | 26篇 |
1977年 | 4篇 |
1975年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
191.
The ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was successfully used as alternative solvent for native chemical ligation of peptide fragments to produce model peptide LYRAXCRANK (X = G, A, L, N, Q, K, and F). The commonly used buffer system including thiol additives such as thiophenol and benzyl mercaptan can be replaced by the nontoxic ionic liquid [C2mim][OAc]. In addition to improving the solubility of the peptides in [C2mim][OAc], yields and rates of the ligation reactions were found to be efficiently enhanced. 相似文献
192.
Rapid quantitative analysis of individual anthocyanin content based on high‐performance liquid chromatography with diode array detection with the pH differential method 下载免费PDF全文
Huayin Wang 《Journal of separation science》2014,37(18):2535-2544
A new quantitative technique for the simultaneous quantification of the individual anthocyanins based on the pH differential method and high‐performance liquid chromatography with diode array detection is proposed in this paper. The six individual anthocyanins (cyanidin 3‐glucoside, cyanidin 3‐rutinoside, petunidin 3‐glucoside, petunidin 3‐rutinoside, and malvidin 3‐rutinoside) from mulberry (Morus rubra) and Liriope platyphylla were used for demonstration and validation. The elution of anthocyanins was performed using a C18 column with stepwise gradient elution and individual anthocyanins were identified by high‐performance liquid chromatography with tandem mass spectrometry. Based on the pH differential method, the high‐performance liquid chromatography peak areas of maximum and reference absorption wavelengths of anthocyanin extracts were conducted to quantify individual anthocyanins. The calibration curves for these anthocyanins were linear within the range of 10–5500 mg/L. The correlation coefficients (r2) all exceeded 0.9972, and the limits of detection were in the range of 1–4 mg/L at a signal‐to‐noise ratio ≥5 for these anthocyanins. The proposed quantitative analysis was reproducible with good accuracy of all individual anthocyanins ranging from 96.3 to 104.2% and relative recoveries were in the range 98.4–103.2%. The proposed technique is performed without anthocyanin standards and is a simple, rapid, accurate, and economical method to determine individual anthocyanin contents. 相似文献
193.
194.
《Arabian Journal of Chemistry》2022,15(12):104363
A magnetic solid-phase extraction technique based on magnetic dendritic structured nanoparticles (Fe3O4@SiO2-NH2-G5) as adsorbent coupled with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) has been developed to detect diazepam, midazolam, zolpidem, and zaleplon in human urine. With Fe3O4@SiO2-NH2 as the central core, dendrimer (G5) grafted alternately with cyanuric chloride and imidazole were bonded to the surface of the core to synthesize Fe3O4@SiO2-NH2-G5. The morphology and structure of the magnetic materials were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and dynamic light scattering (DLS). The key parameters affecting the extraction efficiency were optimized. A satisfactory performance was obtained under the optimum extraction conditions. The proposed method was validated, and the limits of detection of zaleplon, diazepam, zolpidem, and midazolam were 0.05, 0.05, 0.02, and 0.02 ng mL?1, respectively. The linear correlation coefficients r of the four analytes were > 0.996, the intra-day precision was between 2.4 % and 9.4 % with the recoveries between 88.3 % and 104.8 %, and the inter-day precision ranged from 3.9 % to 15.2 % with the recovery in the range of 94.1 %?108.3 %. The magnetic dendritic structure nanomaterial Fe3O4@SiO2-NH2-G5 was successfully used to extract sedative-hypnotic drugs from human urine samples. The Fe3O4@SiO2-NH2-G5-based magnetic solid-phase extraction method eliminates centrifugation and filtration steps as in conventional extraction. Only one step of vortex dispersion extraction could achieve the separation and purification of the target compounds. The proposed method was simple, rapid, environment-friendly, and suitable for the analysis of sedative-hypnotic drugs in human urine. 相似文献
195.
A novel, highly sensitive, simple, and rapid strategy was designed and developed for simultaneous determination of cabozantinib (CBZ) as an anticancer agent and its main metabolites including monohydroxy sulfate (EXEL-1646), N-oxide (EXEL-5162(, amide cleavage product (EXEL-5366), and 6-desmethyl amide cleavage product sulfate) EXEL-1644). Measurements were done through a micellar liquid chromatography (MLC) method coupled with fluorescence detection. The high-performance liquid chromatography (HPLC) was performed using a Kinetex C18 100 Å column as well as acetonitrile, cetyltrimethylammonium bromide (CTAB; 0.2 mol.L?1), and tris buffer (pH 8.5) solutions as the mobile phase at a 40:50:10 (v/v) ratio. The method’s linearity (20 to 700 ng.mL?1), limit of detection (LOD; 2.11 to 3.69 ng.mL?1), limit of quantification (LOQ; 20 to 30 ng.mL?1), intra- and inter-day precisions (RSD < 4.00%), selectivity, recovery, and robustness were fully evaluated. According to the obtained results, the developed method can be used for simple and rapid (~35 min) quantification of CBZ as an anticancer drug and its major metabolites in human serum samples with high sensitivity and low cost. 相似文献
196.
An uncharged, water-soluble per-ethylene-glycol pillar[5]arene derivative ( 1 ) was synthesized and its aggregation mode, host-guest chemistry in water and extraction ability was explored. Compound 1 is a liquid at room temperature; in water, limited self-aggregation occurred at high concentrations as deduced from diffusion NMR and dynamic light scattering. Compound 1 forms pseudo-rotaxane-like 1 : 1 host-guest complexes with 1,ω-di-substituted alkanes with association constants on the order of 103–104 m −1. Interestingly, NMR experiments showed that the guest location relative to the host ring system differs among the different complexes. In proof-of-concept experiments, compound 1 was shown to extract structurally related organic compounds from benzene into water with significant selectivity. Compound 1 , which is a liquid at room temperature and has only limited interactions with its side arms, can, in principle, be regarded as a complement to or as a kind of type I porous liquid. 相似文献
197.
Numerous chemical compounds of high practical importance, such as drugs, fertilizers, and food additives are being commercialized as racemic mixtures, although in most cases only one of the isomers possesses the desirable properties. As our understanding of the biological actions of chiral compounds has improved, the investigation of the pharmacological and toxicological properties has become more and more important. Chirality has become a major issue in the pharmaceutical industry; therefore, there is a continuous demand to extend the available analytical methods for enantiomeric separations and enhance their efficiency. Direct liquid chromatography methods based on the application of chiral stationary phases have become a very sophisticated field of enantiomeric separations by now. Hundreds of chiral stationary phases have been commercialized so far. Among these, macrocyclic glycopeptide-based chiral selectors have proved to be an exceptionally useful class of chiral selectors for the separation of enantiomers of biological and pharmacological importance. This review focuses on direct liquid chromatography-based enantiomer separations, applying macrocyclic glycopeptide-based chiral selectors. Special attention is paid to the characterization of the physico-chemical properties of these macrocyclic glycopeptide antibiotics providing detailed information on their applications published recently. 相似文献
198.
We explore the low-frequency noise of interacting electrons in a one-dimensional structure (quantum wire or interaction-coupled edge states) with counterpropagating modes, assuming a single channel in each direction. The system is driven out of equilibrium by a quantum point contact (QPC) with an applied voltage, which induces a double-step energy distribution of incoming electrons on one side of the device. A second QPC serves to explore the statistics of outgoing electrons. We show that measurement of a low-frequency noise in such a setup allows one to extract the Luttinger liquid constant K which is the key parameter characterizing an interacting 1D system. We evaluate the dependence of the zero-frequency noise on K and on parameters of both QPCs (transparencies and voltages). 相似文献
199.
The linear electrohydrodynamic cylindrical instability of annular Walters B′ viscoelastic dielectric fluid layer surrounded by a conducting gas in the presence of radial electric field is investigated. The obtained dispersion relation is found to be complicated and cannot be treated theoretically easily. Two limiting cases of interest are investigated, when the inertia is dominant, and when both the kinematic viscosity and viscoelasticity are high, and the corresponding new stability conditions are obtained for both cases. We solve the eigenvalue problem numerically using the continuation method which gives better results than the classical non-linear solvers such as Newton and Secant methods. It is found that the applied radial electric field has a dual role on the stability of the considered system, depending of the chosen wavenumbers range. Both the kinematic viscoelasticity and liquid depth are found to have stabilizing effects, while both the kinematic viscosity and surface tension have destabilizing effects on the considered system. The stability or instability breaks down for critical wavenumber values at which the growth rate vanishes. The behaviors of both the maximum growth rate and the corresponding dominant wavenumber are discussed in detail corresponding to the effect of all physical parameters. Finally a comparison between the results obtained here for Walters B′ viscoelastic fluids, and those obtained here too if the fluid is replaced by a Rivlin–Ericksen viscoelastic one is achieved. The limiting cases of absence of electric field and/or kinematic viscoelasticity are also investigated in detail. 相似文献
200.
Victor U. Weiss Natalia Denderz Günter Allmaier Martina Marchetti-Deschmann 《Electrophoresis》2021,42(11):1202-1208
Gas-phase electrophoresis yields size distributions of polydisperse, aerosolized analytes based on electrophoretic principles. Nanometer-sized, surface-dry, single-charged particles are separated in a high laminar sheath flow of particle-free air and an orthogonal tunable electric field. Additionally, nano Electrospray Gas-Phase Electrophoretic Mobility Molecular Analyzer (nES GEMMA) data are particle-number based. Therefore, small particles can be detected next to larger ones without a bias, for example, native proteins next to their aggregates. Analyte transition from the liquid to the gas phase is a method inherent prerequisite. In this context, nonvolatile sample buffers influence results. In the worst case, the (bio-)nanoparticle signal is lost due to an increased baseline and unspecific clustering of nonvolatile components. We present a novel online hyphenation of liquid chromatography and gas-phase electrophoresis, coupling a size-exclusion chromatography (SEC) column to an advanced nES GEMMA. Via this novel approach, it is possible to (i) separate analyte multimers already present in liquid phase from aggregates formed during the nES process, (ii) differentiate liquid phase and spray-induced multimers, and (iii) to remove nonvolatile buffer components online before SEC–nES GEMMA analysis. Due to these findings, SEC–nES GEMMA has the high potential to help to understand aggregation processes in biological buffers adding the benefit of actual size determination for noncovalent assemblies formed in solution. As detection and characterization of protein aggregation in large-scale pharmaceutical production or sizing of noncovalently bound proteins are findings directly related to technologically and biologically relevant situations, we proposed the presented method to be a valuable addition to LC-MS approaches. 相似文献